pubs.acs.

org/macroletters Letter

Loosely Adsorbed Chains Expedite the Desorption of Flattened

Polystyrene Chains on Flat Silicon Surface
Weizhao Ren, Yanlong Li, Yuling Tang, Jianquan Xu,* Cuiyun Zhang, Ophelia K. C. Tsui,
and Xinping Wang*
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ABSTRACT: Herein, the desorption of the adsorbed chains

(including two regions of flattened chains and loosely adsorbed
chains) was examined by monitoring the chain exchange kinetics
Downloaded via BOGAZICI UNIV on January 24, 2024 at 08:53:33 (UTC).

between the adsorbed chains and the top-free chains in a bilayer

system by using fluorine-labeled polystyrene (PS). The results
indicated that the exchange behavior of PS-flattened chains with
the top-free chains is much slower than that of PS-loose chains and
has a strong molecular weight (MW) dependence. Interestingly, in
the presence of loosely adsorbed chains, the desorption of flattened
chains was accelerated greatly and had weaker MW dependency.
We attribute the MW-dependent desorption phenomena to the
average number of contact sites between polymer adsorbed chains
and the substrate, which rapidly increased with increasing MW.
Likewise, the desorption of loosely adsorbed chains may provide extra conformational energy to accelerate the desorption of
flattened chains.

P olymer chains are extremely inclined to adsorb on solid

surfaces since even weak preferential adsorption for
segments adds up to form strong adsorption for a whole
contacts of segment/substrate, even though their interactions
were smaller than kBT (kB is the Boltzmann constant and T is
the temperature).13 Considering the number of segment/
chain. For almost two decades, consensus is emerging that it is substrate contact sites is relatively large, although adsorption is
feasible to tailor the mechanical1−3 and dynamical4−10 still reversible at the segment level, the probability of a
properties of nanomaterials (e.g., substrate supported thin simultaneous detachment of all the adsorbed segments is
polymer coatings and polymer nanocomposites) by regulating extremely low within the time scales at the temperatures of
the structure (or thickness) of the adsorbed chains onto a technological relevance.14,15 That is, the energetic barrier to
nonrepulsive interface. With the development of nano- desorption is very high, so polymer adsorption is considered
technology and the downsizing of material, the importance irreversible.9,16,17 For example, Salatto et al. reported that the
of the adsorbed layer was further increased, and a deeper desorption of polybutadiene-bound chains on carbon black
understanding of it was required. In terms of molecular surfaces (a typical strongly interactive system) was not
motion, the adsorbed chains were generally considered as detected by using neutron spectroscopy.18 Consequently, the
essentially immobile, while this standpoint is being challenged adsorbed layer was referred to as the “dead layer”19−21 in terms
currently. Hence, focusing on the dynamics of adsorbed chains of molecular motion, which leads to a substantially higher glass
is very attractive to fully comprehend the function of the transition temperature (Tg),22,23 lower thermal expansivity,7
adsorbed layer in the nanomaterials from both fundamental dielectric strength,24−26 and capacitance19 than those in bulk
and technological perspectives. polymer material.
Koga et al. have conducted exhaustive research on the However, the standpoint of the adsorbed chain being
structure of the adsorbed polymer layer.11−13 They proposed essentially immobile in terms of molecular motion is being
the formation of a two-layer region of adsorbed chains on a
solid surface, in which chains adopt peculiar conformations
distinct from those of a melt at equilibrium. The inner high- Received: April 6, 2023
density region (i.e., the region with flattened chains) is Accepted: June 13, 2023
associated with an ensemble of chains forming more contacts Published: June 20, 2023
with the substrate, whereas the outer region (i.e., loosely
adsorbed chains) is composed of loosely adsorbed polymers
creating loops.9 Adsorption of polymers can first occur at the

© 2023 American Chemical Society https://doi.org/10.1021/acsmacrolett.3c00206

854 ACS Macro Lett. 2023, 12, 854−859
ACS Macro Letters pubs.acs.org/macroletters Letter

challenged currently.4,7,22,27,28 Several experimental results and

simulation data demonstrate that the adsorbed chains were not
completely frozen, especially for a weakly attractive system.
Napolitano et al.15 declared in his review that the desorption of
adsorbed chains is possible by placing a polymer layer in a pure
solvent though extremely long desorption time is needed and
the desorption rate is almost unmeasurable. It has also been
reported that the detachment of chains from a bound layer
(i.e., adsorbed layer) is possible in polymer nanocomposites by
exploring the isotope adsorption effect, which allows the
displacement of an adsorbed chain with free isotope-labeled
chains.14,29−31 For example, Jimenez29 and Bailey30 found that
the thickness of the bound layer consisted of deuterated chains
of poly(2-vinylpyridine) (dP2VP) decreases when annealed
above a certain high temperature, initiating a time-dependent Figure 1. XPS spectra of PS628-ec-FMA1.5 pristine and regenerated (a)
desorption process. However, the bound layer formed by interfacial sublayer (pristine: hads = 4.5 ± 0.5 nm; regenerated: hads =
hydrogenated P2VP (hP2VP) on silica NPs dispersed in 4.3 ± 0.6 nm) and (b) flattened layer (pristine: hads = 2.1 ± 0.5 nm;
hP2VP melt was not affected32,33 by annealing even at a higher regenerated: hads = 2.0 ± 0.6 nm) on SiO2−Si substrate. The
temperature. Therefore, the understanding of the dynamics of regenerated adsorbed layers were isolated from the corresponding 20
adsorbed chains remains a contradiction and challenging; more nm [PS222]//[PS628-ec-FMA1.5 adsorbed layer] bilayer films after
annealing for 48 h at 403 K (Tg + 30 K). (c) The SFG spectra (ssp) of
experimental results are necessary.
the pristine dPS252 interfacial sublayer and PS-interfacial sublayer
In this paper, a facile method was employed to investigate obtained from the [dPS252]//[PS57 interfacial sublayer] after
the exchange behavior between polystyrene (PS) adsorbed annealing at 403 K for 0 and 48 h. The inset is the schematic of a
chains on the silicon substrate and the top-free chains with a typical bilayer film, including interfacial sublayer and topped layer
fluorine-labeled method. The exchange of PS-flattened chains with free chains.
in the adsorbed layer with top-free PS chains was found to be
more sluggish than that of loosely adsorbed chains and
depends on the molecular weight (MW), annealing temper- regenerated-adsorbed layer to extract the information on
ature, and time. Loosely adsorbed chains in the adsorbed layer chain exchange and desorption. Further details about
result in the accelerated desorption of the flattened chains. experimental methods can be found in the SI.
This study provides new physical insight into the dynamics of Figure 1a displays the XPS spectra of the pristine and
adsorbed chains. regenerated PS628-ec-FMA1.5 interfacial sublayers on SiO2−Si
Polystyrene samples of PSm (3 ≤ Mw = m ≤ 222 kg/mol, substrates, which were isolated from the PS628-ec-FMA1.5 film
the polydispersity indices (PDI) were <1.10) and deuterated and [PS222]//[PS628-ec-FMA1.5 interfacial sublayer] bilayer
polystyrene (dPS; Mw = 252 kg/mol, PDI = 1.05) were films, respectively. The results suggested that the F/C ratio of
obtained from Polymer Source Inc. (Canada). PS end-capped the regenerated interfacial sublayer is 0.05, which significantly
with 2-perfluorooctylethyl methacrylate (FMA) units (PSx-ec- decreased from that of pristine interfacial sublayer (∼0.33).
FMAy, 30 ≤ x ≤ 628, y = 1−2, PDIs < 1.18, the subscript is a Figure S2a demonstrates that the F/C ratio on the surface of
degree of polymerization) were prepared by atom-transfer the bilayer film of the [PS222]//[PS628-ec-FMA1.5 interfacial
radical polymerization (ATRP) method.34,35 As reported sublayer] changes from 0 to 0.15 after 48 h of annealing at 403
previously,12,36−39 the pristine-adsorbed layer with both K, confirming that the fluorine-labeled chains can migrate to
flattened and loosely adsorbed chains (called interfacial the surface of the bilayer sample. That is, the chains in the
sublayer) or flattened chains only (called flattened layer) was interfacial sublayer are not “dead” and could desorb and
obtained by leaching the annealed PS films (thickness >120 migrate from the substrate. Considered that the thicknesses of
nm, silicon (100) substrate (SiO2−Si), Tg + 50 K for 72 h) in the pristine (hads = 4.5 ± 0.5 nm) and regenerated (hads = 4.3 ±
toluene or chloroform,37,39 respectively. See the detail in 0.6 nm) interfacial sublayer are the same within experimental
Figure S1 of the Supporting Information (SI). uncertainty, this indicated the occurrence of chain exchange
The bilayer films described as [PS]//[PS-ec-FMA interfacial between the adsorbed and free chains. The XPS spectra of the
sublayer] (or [PS-ec-FMA]//[PS interfacial sublayer], from pristine and regenerated PS628-ec-FMA1.5 flattened layer, which
left to right corresponds to free surface to substrate) and were isolated from the PS628-ec-FMA1.5 film and [PS222]//
[PS]//[PS-ec-FMA flattened layer] (or [PS-ec-FMA]//[PS [PS628-ec-FMA1.5 flattened layer] bilayer films, respectively, are
flattened layer], [dPS]//[PS interfacial sublayer]) were plotted in Figure 1b. In contrast, the F/C ratio kept almost the
generated by spin-coating a toluene solution of PS onto the same after annealing, indicating that the flattened layer was
prepared PS interfacial sublayer and flattened layer, respec- unable to exchange within the measured temperature and time
tively. The inset of Figure 1c shows the schematic of a typical scale, as further corroborated by the fact that also no fluorine
bilayer film including an interfacial sublayer and a topped layer. signal was detected on the bilayer film surface after annealing
After annealing the bilayer films for chain desorption, the (Figure S2b). In order to eliminate the possible effect of the
regenerated interfacial sublayers or flattened layers were also fluorinated groups in flattened layer on chain exchange, the
obtained by leaching the bilayer in toluene or chloroform (see bilayer sample consisting of an ∼80 nm [PS628-ec-FMA1.5]//
the details in Figure S1). The F/C ratios and sum SFG signals [PS57 flattened layer] was also prepared, and a similar result
were detected by X−ray photoelectron spectroscopy (XPS) was obtained. These results suggested that the desorption of
and sum frequency generation spectroscopy (SFG), respec- polymer chains only occurs in the interfacial sublayer at this
tively, for the pristine-adsorbed layer and corresponding conducted experimental conditions.
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ACS Macro Lett. 2023, 12, 854−859
ACS Macro Letters pubs.acs.org/macroletters Letter

To further confirm the chain exchange behavior in the displacement by poly(methyl methacrylate) than long chains.
interfacial sublayer, the surface-sensitive technique SFG was Considering that the average number of chain/solid contacts
employed. Figure 1c shows the ssp SFG spectra for the for adsorbed polymer chains was ∼N1/2 (N degree of
interfacial sublayer obtained from the bilayer film of polymerization),43,44 the value of tfe as a function of the N1/2
[dPS252]//[PS57 interfacial sublayer]40,41 after annealing at for adsorbed polymers was plotted in Figure 2d to explore the
403 K for different annealing times (tan). It was found that no relationship between the exchange behavior and the number of
SFG signal was detected at tan = 0 h. A peak at 2288 cm−1, chain/solid contact sites. The observation revealed that tfe
which corresponds to the ν2 vibration mode of deuterated 1/2
increased exponentially with increasing N1/2 (tfe ∼ eN ), whichd

phenyl rings,41,42 appeared at tan = 48 h, so does in pristine is ascribed to the probability that all the adsorbed segments in
dPS-interfacial sublayer. These spectral features confirmed that one chain are desorbed at the same time and will decrease
PS chains in the interfacial sublayer will desorb, while the dPS
exponentially. That is, the chain exchange kinetics was
chains in the top layer will exchange to the corresponding
significantly suppressed with a slight increase in the number
empty sites in the interfacial sublayer during annealing.
of contact sites, including reversible equilibrium between
The question whether the flattened chains can desorb from
desorption and adsorption and consequent cooperative action.
substrate or not was explored for stronger experimental
Higher annealing temperatures and longer annealing time
conditions: higher annealing temperature, longer annealing
would increase the probability that the flattened chains could
time, and lower MW. The XPS spectra of the regenerated PS-
undergo complete desorption if the polymer chain was not
flattened layers, which were obtained by chloroform leaching
degraded at this situation, which was supported by certain
after annealing the [PS30-ec-FMA1.3]//[PS3 flattened layer]
previously reported results.31 The AFM height images of the
and [PS268-ec-FMA2]//[PS20 flattened layer] bilayer at Tg +
pristine and regenerated flattened layers with various MW are
60 K for various time, were displayed in Figure 2a,b. It is found
displayed in Figure S4. The results showed that the surface
morphology of the regenerated flattened layers was nearly
identical to that of the pristine flattened layer, as well as their
thicknesses (data not shown). These results further indicated
that the change of F/C ratio in the flattened layer was driven
by the exchange of the flattened chains with the free chain in
the top layer, instead of simple chain adsorption from the top
layer.
Interestingly, an unexpectedly accelerated desorption of the
flattened chains was observed in the presence of loosely
adsorbed chains. Figure 3 shows the XPS spectra of the
regenerated flattened layer on the SiO2−Si substrate obtained
from [PS628-ec-FMA1.5]//[PS57 interfacial sublayer] and
[PS628-ec-FMA1.5]//[PS57 flattened layer] bilayer films.
Notably, no fluorine groups existed in the pristine flattened
layer, while the fluorine signal was detected in the regenerated
flattened layer after annealing at Tg + 50 K for 48 h in the
presence of loosely adsorbed chains (Figure 3a). However, in
the absence of loosely adsorbed chains, no fluorine signal was
observed in the regenerated flattened layer, even after 120 h at
Figure 2. F1s region of XPS spectra of the regenerated PS-flattened Tg + 70 K (Figure 3b). This finding clearly revealed that the
layer obtained from (a) [PS30-ec-FMA1.3]//[PS3 flattened layer], (b) loosely adsorbed chain in the interfacial sublayer could
[PS268 -ec-FMA2 ]//[PS20 flattened layer], and (c) [PS628 -ec- significantly stimulate the exchange of the flattened chains
FMA1.5]//[PS-flattened layer]. For (a) and (b), the bilayer films with the free chains in the top layer.
were annealed at Tg + 60 K for different time. For (c), the bilayer The effect of PS’s MW in the interfacial sublayer on the
films were annealed at Tg + 70 K for 120 h and 57 ≤ MW ≤ 222 kg/ desorption of the flattened chains was investigated. Figure 4a,b
mol. (d) The time for the flattened layer to begin exchanging (tfe) as a
function of the N1/2 of adsorbed polymers.
displayed the representative XPS spectra within the F1s area of
the regenerated flattened layer with different MW after
annealing at Tg + 70 K for various times. The values of tfe
that fluorine signal could be observed after annealing enough
were observed to be ∼9 ± 3 and ∼125 ± 5 h, corresponding to
time. That is, although the activated condition is more
MW of 57 and 156 kg/mol, respectively. Compared with the
extreme, the flattened chains are also not “dead”. Furthermore,
result shown in Figure 2c, it was evident that the presence of
the incubation time for the flattened layer to begin exchanging
(tfe) increased with MW and was ∼0.25 ± 0.25 h and 48 ± 2 h loosely adsorbed chains increased the mobility of the flattened
for MW = 3 and 20 kg/mol, respectively. Moreover, it was chains, resulting in easier chain desorption and exchange.
checked that the MW of the top layer will not affect the value Figure 4c displays the value of tfe as a function of N1/2 for
of tfe, which means tfe is determined by the MW of flattened adsorbed chains. It was found that tfe increased linearly with
chains; see Figure S3. When the MW was >57 kg/mol, no N1/2 in the region of 57 < Mn < 156 kg/mol, while tfe increased
1/2
chain exchange was observed despite the bilayer samples being exponentially (tfe ∼ eN ) in the absence of loosely adsorbed
d

annealed for 120 h at Tg + 70 K (Figure 2c). This strong MW chains, as shown in Figure 2d. In addition, the desorption and
dependency was similar to the results of desorption and exchange of the flattened chains could only be observed when
adsorption in polymer solution reported by Granick.37 They MW was <20 kg/mol for the [PS-ec-FMA]//[PS-flattened
discovered that short PS chains were more susceptible to layer], whereas chain exchange was easily observed up to 156
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ACS Macro Lett. 2023, 12, 854−859
ACS Macro Letters pubs.acs.org/macroletters Letter

Figure 3. Schematic of the preparation process and the XPS spectra of the regenerated flattened layer on the SiO2−Si substrate obtained from (a)
the [PS628-ec-FMA1.5]//[PS57 interfacial sublayer] (annealed at Tg + 50 K for 48 h) and (b) the [PS628-ec-FMA1.5]//[PS57 flattened layer]
(annealed at Tg + 70 K for 120 h).

Figure 4. F1s region of the XPS spectra of the regenerated PS-flattened layer obtained from the bilayer films of (a) [PS628-ec-FMA1.5]//[PS57
interfacial sublayer] and (b) [PS628-ec-FMA1.5]//[PS156 interfacial sublayer] after annealing at Tg + 70 K for different time. (c) The time for the
flattened layer to begin exchanging (tfe) as a function of the N1/2 for flattened chains.

kg/mol for the [PS-ec-FMA]//[PS interfacial sublayer] system. Since the loosely adsorbed chain was easily desorbed due to
Thus, the desorption of the flattened chains was significantly relatively few adsorbed sites with the substrate, its desorption
enhanced by loosely adsorbed chains in the interfacial sublayer. and diffusion may drive the desorption of the corresponding
Why did loosely adsorbed chains cause accelerated flattened chain through entanglement. (2) From the
desorption and exchange of flattened chains in the sublayer perspective of thermodynamics for desorption, the change of
of the interface? The cause could be comparable to the enthalpy for the system of single flattened chains, which is
bonding of NPs grafted with numerous DNA. While the base- determined by the polymer/substrate interactions and
pairing transition of a single chain happens over a temperature adsorbed chains packing, is similar to the system of interfacial
range of 30−40 K, the cooperativity associated with the sublayer. However, the desorption entropy change for the
binding of many chains sharpens this “transition” to occur interfacial sublayer is larger than the flattened layer since the
within 5 K.44 This cooperative effect should be the result of loosely adsorbed chains also contribute to the variation of
short-range duplex-to-duplex interactions, which resulted in a entropy. That is, the interfacial sublayer has higher conforma-
greater transition enthalpy due to the presence of numerous tional energy46 than single flattened layer and presents easier
DNA as linkages between pairs of particles. The difference in desorption. These findings may provide important physical
enthalpy with adsorption/desorption was attributed to the insights into the mobility of the adsorbed chains on the solid
energy exchange on pinning/unpinning monomers at the substrate and the consequent effect of substrate or filler on the
polymer/substrate interface and the conformational modifica- dynamics of nanoconfined thin polymer films and polymer
tions underlying the liquid−liquid transition between adsorbed nanocomposites.
and desorbed polymer. Napolitano31 reported the former In summary, the desorption behaviors of the PS-adsorbed
contribution in poly(4-tert-butylstyrene) is limited to only 6% chains (i.e., loosely adsorbed chains and flattened chains) on
of the total enthalpy exchanged and the vast majority of the the SiO2−Si surface with the top free chains were investigated
enthalpy exchange resulting from the adsorption/desorption by monitoring the F/C ratio of PS-adsorbed layer with
transition must be attributed to a variation in conformational annealing time using XPS and a fluorine-labeled method. The
energy. Therefore, the induced flattened chain desorption by results suggested that the desorption of PS-flattened chains was
the loosely adsorbed chain could be the result of two much slower than that of PS-loosely chains and strongly
contributions. (1) During the formation of interfacial sublayer, correlated with molecular weight, occurring only at relatively
the flattened chains and loosely adsorbed chains are both low molecular weights. Such strong MW-dependent desorption
formed so that the entanglements between them occurs12,45 could be dominated by the average number of contact sites
with high probability under chain conformation adjustment. between polymer chains adsorbed on the substrate (∼N1/2), as
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ACS Macro Lett. 2023, 12, 854−859
ACS Macro Letters pubs.acs.org/macroletters Letter

the exponential increase of the time for the flattened layer to https://pubs.acs.org/10.1021/acsmacrolett.3c00206
1/2
begin exchanging (tfe) with N1/2 (tfe ∼ eN ) was observed.
d

However, it was quite interesting that the loosely adsorbed Author Contributions
chains in the interfacial sublayer significantly accelerated the Conceptualization: J.X., C.Z., and X.W.; Methodology: J.X.,
desorption of flattened chains. In addition, tfe increased linearly W.R., and X.W.; Investigation: J.X., W.R., Y.L., and Y.T.;
with increasing N1/2 concentration in the presence of loosely Visualization: J.X., W.R., and C.Z.; Supervision: X.W. and
absorbed chains. The accelerated desorption of flattened O.K.C.T.; Writing−original draft: J.X. and W.R.; Writing−
chains was ascribed to the desorption of loosely adsorbed review and editing: J.X., X.W., and O.K.C.T.
chains could contribute extra conformational energy, resulting Notes
in a greater entropy variation for the desorption. These The authors declare no competing financial interest.
findings provide crucial physical insight into the mobility of the
adsorbed chains and the reverting thermodynamic state at the
interface. ■ ACKNOWLEDGMENTS
We acknowledge the supports of the National Natural Science
■
*
ASSOCIATED CONTENT
sı Supporting Information
Foundation of China (Nos. 22173081, 22161160317, and
22203075), the Fundamental Research Funds of Zhejiang Sci-
Tech University (No. 22062313-Y), and the Foundation of
The Supporting Information is available free of charge at
Zhejiang Sci-Tech University (No. 21062110-Y).
https://pubs.acs.org/doi/10.1021/acsmacrolett.3c00206.
(1) The detail of measurement methods; (2) The
characterizations on the rinsing and structure of the
pristine flattened layer and interfacial sublayer; (3) XPS
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