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Improved Self-Assembly of Poly(dimethylsiloxane-b-ethylene oxide)

Using a Hydrogen-Bonding Additive

Yingdong Luo,1,2 Bongkeun Kim,1 Damien Montarnal,1,3* Zoltan Mester,4 Christian W. Pester,1
Alaina J. McGrath,1 Glake Hill,5 Edward J. Kramer,1,6,7 Glenn H. Fredrickson,1,6,7
Craig J. Hawker1,2,6
1
Materials Research Laboratory, University of California, Santa Barbara, California 93106
2
Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106
3
Laboratoire de Chimie Catalyse Polymeres et Procedes (C2P2), Universite
 de Lyon 1, CPE Lyon, CNRS, UMR 5265, Villeurbanne,
France
4
Department of Chemical and Biological Engineering, Princeton University, New Jersey 08544
5
Department of Chemistry and Biochemistry, Jackson State University, Jackson, Mississippi 39217
6
Materials Department, University of California, Santa Barbara, California 93106
7
Department of Chemical Engineering, University of California, Santa Barbara, California 93106
Correspondence to: C. J. Hawker (E - mail: hawker@mrl.ucsb.edu) or G. H. Fredrickson (E - mail: ghf@mrl.ucsb.edu)

Received 20 January 2016; accepted 23 February 2016; published online 17 March 2016
DOI: 10.1002/pola.28093

ABSTRACT: Block copolymers with increased FloryHuggins
interaction parameters (v) play an essential role in the produc-
tion of sub-10 nm nanopatterns in the growing field of directed
self-assembly for next generation lithographic applications. A
library of PDMS-b-PEO block copolymers were synthesized by
click chemistry and their interaction parameters (v) determined.
The highest v measured in our samples was 0.21 at 150 8C,
which resulted in phase-separated domains with periods as
small as 7.9 nm, suggesting that PDMS-b-PEO is a prime candi-
the amount of LTA in the blend increased, allowing for further
control over self-assembly. To understand the mechanism of
this phenomenon, we present a novel field-based supramolec-
ular model, which describes the formation of copolymer-
additive complexes by reversible hydrogen bonding. The
mean-field phase separation behavior of the model was calcu-
lated using the random phase approximation (RPA). The RPA
analysis reproduces behavior consistent with an increase of
the effective v in the PDMS-b-(PEO/LTA suprablock). V C 2016

date for sub-10 nm nanopatterning. To suppress PEO crystalli-
zation, PDMS-b-PEO was blended with (L)-tartaric acid (LTA)
which allows for tuning of the self-assembled morphologies.
Additionally, it was observed that the order-disorder transition
temperature (TODT) of PDMS-b-PEO increased dramatically as
Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem.
2016, 54, 22002208
KEYWORDS: block copolymer; lithography; click chemistry; poly-
mer blend; supramolecular assembly; phase separation

INTRODUCTION For the semiconductor industry, directed
self-assembly (DSA) or block copolymer lithography offers a
promising complement or alternative to emerging patterning
technologies, such as extreme UV lithography (EUV).17 Key
to the success of these approaches is the self-assembly of AB
diblock copolymers 813 with parameters governing morphol-
ogy including the overall degree of polymerization (N), the
relative volume fraction of each individual block (f), and the
FloryHuggins interaction parameter, v (T21).14 The latter
is a measure of the incompatibility between the A and B
blocks, which in turn determines the domain periods, d, of
self-assembled morphologies according to the formula dv1/
6 2=3 15,16
N: Therefore, decreasing the size of the domain in
order to shrink feature sizes for lithographic applications17
requires that the polymer chains be lower in molecular
weight (decreased N) and consequently the polymer blocks
need stronger incompatibilities (higher v) to maintain segre-
gation strengths large enough to achieve self-assembly

Yingdong Luo and Bongkeun Kim contributed equally to this work.

Edward J. Kramer passed away on December 27, 2014.
*Present address: Damien Montarnal, Universite Lyon 1, CPE Lyon.

Additional Supporting Information may be found in the online version of this article.
C 2016 Wiley Periodicals, Inc.
V

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(vN > 10.5). A high v parameter therefore plays an important
role in shrinking feature size in directed self-assembly (DSA)
lithography, allowing one to order sub 10 nm self-assembled
morphologies by manipulating substrate topology and chem-
istry. Examples include contact hole shrink,1822 and line-
space patterns from grapho-epitaxy7,13,2327 and chemo-
epitaxy.2831
Poly(styrene-b-methyl methacrylate) (PS-b-PMMA) is the cur-
rent industrial and academic standard for patterning applica-
tions due to facile selective etching of PMMA by UV
irradiation and the ready availability of PS-b-PMMA diblock
copolymers.32 Further, nearly balanced interfacial interac-
tions with the free surface33 enable perpendicular morpholo-
gies to be prepared.34 PS-b-PMMA, however, suffers from a
low v parameter ( 0.04 at 150 8C), limiting the smallest
obtainable feature sizes to around 20 nm.35 With demand
for ever smaller domain sizes within the semiconductor
industry, intense research has been focused on high v block
copolymers for nanopatterning. High v candidates include,
but are not limited to, poly(dimethylsiloxane) (PDMS)
based,25,3638 polytrimethylsilylstyrene (PTMSS) based,3941
and polyhedral oligomeric silsesquioxane (POSS) based
BCPs31,4245 with all systems having high contrast in oxygen
plasma etching and inherently low compatibility with organic
polymers. For PDMS-based systems, commercially available
PDMS-b-PS has been widely studied for DSA lithography
leading to 10 nm pitch size12,25,4648 and we recently
reported sub-10 nm patterns for PDMS-b-PMMA.49
In this study, we sought to access even smaller nanoscale
features by further increasing v. PDMS-b-PEO was chosen
based on the amphiphilic nature and synthetic accessibility.
However, one major drawback of PEO-containing BCPs is the
crystalline nature of PEO, which can be detrimental to the
formation of well-ordered nano-structures. To address this
challenge, Watkins has elegantly demonstrated that blending
with hydrogen-bond donating polymers and small molecules
can suppress PEO crystallinity and simultaneously enhance
self-assembly.5054 We present a synthetic and theoretical
approach based on reversible association to increase our
understanding of how hydrogen-bond donating small mole-
cules influence the effective interaction parameter of PDMS-
b-PEO. By blending PDMS-b-PEO with (L)-tartaric acid, crys-
tallization of PEO is successfully inhibited and effective v
simultaneously increased. In addition, recent theoretical
studies based on a field theoretic model have considered
reversibly bonded copolymer melts, for example, supramo-
lecular diblock55 and triblock,56 binary difunctional poly-
mers,57 and multifunctional supramolecular networks.58
Here, we build on these studies to treat site-specific interac-
tions along the polymer backbone and account for the asso-
ciation of PEO with hydrogen-bonding small molecule
additives. For simplicity, we employ a coarse-grained bead
spring model15 to represent monomer species and small
molecule additives alike. With this model, the spinodal phase
boundaries of the block copolymer blends and small mole-
cule additives are obtained and the FloryHuggins parame-
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ters between the PDMS and PEO/LTA supra block and the
PDMS and free LTA molecules determined.
EXPERIMENTAL
Materials and Methods
Unless otherwise noted, all reagents were used as received
from Sigma-Aldrich. Synthesis of x-Azido-PDMS and x-
Alkynyl-PEO are summarized in the Supporting Information.
Nuclear magnetic resonance spectra were recorded on either
a Varian 500 MHz, or a Varian 600 MHz instrument. All 1H
NMR experiments are reported in chemical shift, d, units,
parts per million (ppm), and were measured relative to the
signal for residual chloroform (7.26 ppm) in CDCl3, unless
otherwise stated. Size exclusion chromatography (SEC) was
performed on a Waters 2695 separation module with a
Waters 2414 refractive index detector in chloroform with
0.25% triethylamine as the eluent. Number average molecu-
lar weights (Mn), weight average molecular weights (Mw),
and polydispersities (Mw/Mn) were calculated relative to lin-
ear polystyrene standards. Microwave reactions were per-
formed in an Initiator Eight Microwave System (Biotage).
Small Angle X-Ray Scattering
Small angle X-ray scattering (SAXS) measurements of bulk
samples were conducted using a custom constructed SAXS
instrument. The instrument used a 50 micron microfocus, a
Cu target X-ray source (k 5 1.57 ) with parallel beam multi-
layer optics and monochromator (Genix from XENOCS SA,
France), high efficiency scatterless hybrid slits collimator
developed in-house, and a Detris Pilatus 100 K hybrid pixel
detector. The typical q range for the measurement spans
0.010.25 21. Samples for SAXS were melt-pressed inside a
metal washer and annealed in a vacuum oven (20 mTorr, 70
8C) for the designated amount of time. The metal washer
was then carefully sealed with a Kapton film on both sides
with epoxy glue.
General Procedure for Preparing a PDMS Diblock
Copolymer by Copper Nanoparticle Catalyzed Click
Reaction
A 5 mL microwave reaction tube was charged with 5 mL of
toluene, copper nanoparticles (8.0 mg, 0.12 mmol), x-
alkynyl-PEO (Mn 5 2 kDa, 200 mg, 0.1 mol, 1 equivalent),
and its counterpart, x-azido-PDMS (Mn 5 1.7 kDa, 187 mg,
0.1 mmol, 1.1 equivalent).49 The mixture was kept at 150 8C
for 1 h in the Biotage microwave reactor. The reaction mix-
ture was filtered by 0.45 lm PTFE syringe filter. The filtrate
was then centrifuged at 3000 rpm for 5 min. A clear top
layer was carefully decanted and concentrated. Flash chro-
matography was performed in order to remove the excess
PDMS. The excess PDMS homopolymer was removed first by
eluting with CH2Cl2. PDMS-b-PEO was then obtained by
using MeOH/CH2Cl2 (v/v 5 1/10) as the eluent. The fractions
were combined, concentrated and dried under high vacuum
to yield pure diblock copolymer with a typical yield of 50
80%. Representative 1H NMR (500 MHz, CDCl3-d1, d): 7.53
(s, 1H, triazole), 4.68 (s, 2H, -O-CH2-triazole), 4.31 (t, 2H,
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FIGURE 1 Schematic illustration of the PDMS-b-PEO (DO)
block copolymer structure and the corresponding bead-spring
model. A (gray), B (blue), C (red), and D (purple) circles stand
for beads representing coarse-grained monomers of PDMS,
PEO, (L)-tartaric acid, and PEO-tartaric acid complex, respec-
tively. The reversible reaction of hydrogen bond is described
as B1C
D. [Color figure can be viewed in the online issue,
which is available at wileyonlinelibrary.com.]
PDMS-(CH2)2-CH2-triazole), 3.67 3.61 (m, PEO backbone),
3.38 (s, 3H, CH3O-PEO), 1.95 1.88 (m, 2H, PDMS-CH2-CH2-
CH2-triazole), 1.59 1.50 (m, 1H, CH3-CH(PDMS)-CH(H)CH3),
1.19 1.09 (m, 1H, CH3-CH(PDMS)-CH(H)CH3), 0.96 0.89
(m, 6H, CH3-CH(PDMS)-CH(H)CH3), 0.57 0.49 (m, 3H, CH3-
CH(PDMS)-CH2CH3 and PDMS-CH2-CH2-CH2-triazole), 0.20
20.07 (m, PDMS backbone).
Bead Spring Field-Theoretic Model
To describe the reversible site-specific interaction of PEO
and LTA, we used a bead-spring model in the framework of
self-consistent field theory (SCFT).15 In this model, the num-
ber of beads along the chains is kept constant during the
reaction between PEO (B) and (L)-tartaric acid (C) (see Fig.
1), but each type B (PEO) bead gains volume and changes its
interactions with the other components when a C molecule
(LTA) is bound to it (state D). To determine the stability of
the disordered phase against microphase separation and
extract a shift in the effective v associated with LTA binding,
the random phase approximation (RPA)14 was used. RPA has
the advantage of simplifying the SCFT model and, thus,
allowing for the efficient analysis of the phase behavior of
our system. The PDMS block is represented as a series of
beads that we term species A, connected by linear entropic
springs. Each bead occupies a volume vA 51/q0, where q0 is
the total density (of all types of beads) in the blend. The
root-mean-square length of a spring is the statistical segment
length b and we adopt b/61/2 as the reference unit of length.
The polar block (PEO) is represented by a series of beads
denoted B. The beads occupy the same volume as the type
A beads (vB 5 vA) and are connected by entropic springs
with the same harmonic bond potentials as in the A block.
The diblock is immersed in a solvent of free (non-polymer-
ized) C (tartaric acid) beads that we assume to have the
same volume as the A and B beads. The C beads reversibly
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bind to B beads on the diblock to form D beads of increased
size on a new effective diblock. During this event, the overall
volume is conserved; for example, the volume of a D is twice
the volume of an individual B or C bead. We further assume
that the solution is incompressible.
To describe the chemical equilibrium of hydrogen bonding, it
is convenient to work in the grand canonical ensemble. The
activity of the AB diblock is defined as zAB and the activity of
the C solvent is defined as zC. The activity of a diblock with
nC beads attached to produce nD beads is denoted by zABn.
Expressions for zABn are constructed from the following
equations of chemical equilibrium:
zAB1
5Keq ) zAB1 5zAB zC Keq ;
zAB zC
zAB2
5Keq ) zAB2 5zAB1 zC Keq ;
zAB1 zC (1)
zABn
5Keq ) zABn 5zABn21 zC Keq
zABn21 zC
where Keq is the equilibrium constant and it is assumed that
binding events are uncorrelated between different sites. We
see that once Keq, zAB, and zC are specified, all of the deriva-
tive activities of the reaction products are uniquely deter-
mined. However, the constraint of incompressibility further
renders only one of the two fundamental activities independ-
ent, so we make the simple
 choice
 of the arbitrary constant,
zC and define Keq 5exp 2 DGH2bonds , where DGH2bonds 525:0 k
RT
J=mol approximately from the general ether oxygen and
hydrogen from carboxylic acid,59,60 so that the binding of C
beads toward B is preferential.
Pairwise interactions between non-bonded beads are speci-
fied by FloryHuggins parameters where L 6 K and L5
fA; B; C; Dg and K5fA; B; C; Dg in all cases. vAB is fixed from
experimental measurement on the pure diblock and vBC, vBD,
and vCD are set to zero as B and C make hydrogen bonds
and form D. vAC and vAD are iteratively derived from the RPA
modeling by fitting to experimental TODT data as described
in Supporting Information 2. The binary interactions and
incompressibility constraint in the grand partition function
are decoupled with auxiliary fields, transforming the
particle-based model into a statistical field theory according
to well-established techniques.15 A saddle point (mean-field)
approximation to that theory leads to a set of self-consistent
field theory (SCFT) equations for the associating diblock
model. The relevant expressions are developed in the Sup-
porting Information 1A.
Random Phase Approximation
The spinodal or stability limit of the homogeneous blend
against microphase separation, which is very close to the
order-disorder transition envelope predicted by SCFT, can be
found by a simplification of the SCFT equations known as
random phase approximation (RPA).14,61 This method will
suffice in the present paper for predicting the role of solvent
association on TODT and identifying an effective interaction
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TABLE 1 Characterization Data Summary for PDMS-b-PEO behavior investigated by differential scanning calorimetry
Copolymers (DSC), as shown in Figure 2. During the heating cycle, pure
D2.2O5.0 showed a strong endothermal peak due to the melt-
Samplea Mn - b
D Dc Mord d0e (nm) TODTf (8C) ing of PEO crystallites [Fig. 2(A)]; upon cooling, the corre-
D1.1O1.9 3.0 1.08 41% (lam) 7.9 80 sponding exothermal crystallization peak was observed [Fig.
2(B)]. Both peaks dramatically decreased and shifted to
D1.1O2.1 3.0 1.08 38% (lam) 8.1 80
lower temperatures when D2.2O5.0 was blended with either 5
D1.7O2.0 3.7 1.10 50% lam 10.2 175
or 10 wt % LTA, indicating an effective partial suppression
D2.2O5.0 7.2 1.04 34% lam 15.3 n/a of PEO crystallization. Significantly, no crystallization peak
D9.0O1.8 10.8 1.07 86% bcc 14.4 n/a was observed in the cooling curve when using 15 wt % or
a
greater LTA. Instead, glass transitions at 230 to 250 8C
Sample name refers to the components (D 5 PDMS; O 5 PEO) and sub-
scripts refer to the number average molecular weight (in thousands) of were observed in both cooling and heating curves, suggest-
each block. ing the formation of a glassy PEO/LTA complex. Although a
b -
D is polydispersity, Mw/Mn. cold crystallization and corresponding melting event were
c
fD is volume fraction of PDMS, calculated based on monomer volume
of each block. m(PDMS) 5 0.138 nm3,65 m(PEO) 5 0.069 nm3.65
observed above the glass transition in each heating curve
d
Mor refers to morphology, which was determined by the q-ratios of
SAXS peak positions. Lam and bcc indicate lamellar and body centered
cubic (bcc) sphere morphologies, respectively. (Lam) refers to morphol-
ogies classified as lamella based on the volume fraction of PDMS, but
the secondary peaks were not observed in SAXS.
e
Domain periods were calculated by d0 5 2p/q*, where q* is the posi-
tion of the primary Bragg reflection.
f
Details of order-disorder transition temperature measurements are
summarized in the Supporting Information.

parameter for the PEO/LTA suprablock with PDMS. Here, we

extend the approach of Mester et al.58 in transforming the
bead-spring SCFT model15 into an RPA expression for the
multicomponent polymer system.62,63 Unlike RPA calcula-
tions for non-reactive block copolymers, in the present
model the concentrations of species and auxiliary fields in
the homogeneous base state must be computed numerically
using the self-consistent field equations. For this purpose a
Newton-Raphson method64 is used. An analytical linear anal-
ysis about this base state leads to equations described in the
Supporting Information 1B and 1C that can be used to iden-
tify the spinodal instability to microphases. We use this sta-
bility limit as a proxy for the order-disorder transition.

RESULTS AND DISCUSSION

Based on our synthetic experience preparing PDMS-b-PMMA,49

we used facile and modular azide-alkyne click chemistry to
prepare a library of pure PDMS-b-PEO diblock copolymers with
different molecular weights and narrow polydispersities. Poly-
mer details are presented in Figure 1 and Table 1. Successful
coupling of the two blocks was confirmed by 1H NMR (Sup-
porting Information Fig. S1), and by size exclusion chromatog-
raphy (SEC), showing a clear shift in retention time towards
higher molecular weights and the absence of any homopolymer
(Supporting Information Fig. S2).

For PDMS-b-PEO block copolymers to be useful materials for

nanopatterning applications, the overriding crystallization of
the PEO domains must be suppressed. Inspired by studies in
which the crystallization of PEO was controlled by blending
with hydrogen-bonding polymers51 and small molecules,52,53
PDMS-b-PEO (D2.2O5.0) was initially combined with various
amounts of (L)-tartaric acid (LTA) and the crystallization
FIGURE 2 Differential scanning calorimetry profiles of D2.2O5.0
blended with different amounts of (L)-tartaric acid: (A) cooling
curve; (B) heating curve. Exothermal peak is positive (up). Crys-
tallization of PEO was effectively suppressed by LTA.

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FIGURE 3 Small angle X-ray scattering profiles of D1.7O2.0
blended with different amounts of (L)-tartaric acid. The num-
bers designate the weight percent of LTA in the melt. L/C refer
to lamellar or cylindrical morphologies.
using 1525 wt % LTA, crystallization events were com-
pletely absent in blends containing more than 30 wt % LTA,
demonstrating efficient suppression of PEO crystallization.
The ability to control PEO crystallinity allows the domain
periodicities and morphologies of neat PDMS-b-PEO BCPs
and their blends with LTA to be investigated by SAXS. At
room temperature, all neat PDMS-b-PEO BCPs showed a
broad primary scattering peak due to the presence of PEO
crystallites with a broad distribution of grain sizes. These
crystallites disrupt microphase separation. Upon heating the
samples above the melting point of PEO (60 8C), this peak
was replaced by a new set of well-defined scattering peaks,
suggesting the existence of well-ordered nanostructures. The
domain periods were calculated via d0 5 2p/q* (q* is the
position of the principal SAXS peak), and produce values
below 15 nm for all samples (see Table 1). These domain
periods are much smaller than domain period of PS-b-PMMA,
the current industry standard in DSA lithography. Remarkably,
D1.1O1.9 self-assembled to form lamellae with d0 as low as
7.9 nm, one of the smallest domain periods reported for the
self-assembly of a linear diblock copolymer.43,66,67 From the
ratio of scattering reflections, the underlying morphologies for
D1.7O2.0 and D2.2O5.0 (lamellar) and D9.0O1.8 (body-centered
cubic spheres) were observed (Table 1). Higher order scatter-
ing peaks were not detected for D1.1O1.9 and D1.1O2.1 due to
the low overall molecular weight (see the Supporting Informa-
tion for additional information on SAXS profiles and
morphologies).
On a molecular level, addition of LTA to the diblock copoly-
mers leads to an increase in the effective molar volume of
the PEO repeat units and a corresponding change in the
effective molecular volume of the PEO block and domain
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periods. These changes were observed as shown in Figure 3
with the principal scattering peak shifting to smaller q
(larger domains) as the amount of LTA increases. SAXS
experiments on the blends were carried out at 60 8C to
exclude any influence of PEO crystallinity and corroborates
domain size expansion resulting from the formation of a
supramolecular block between LTA and PEO.53
Having demonstrated that the assembly of low molecular
weight, highly immiscible PDMS-b-PEO block copolymers can
be tuned by the addition of H-bonding additives, a theoreti-
cal understanding was sought. Initially, the block copolymer
was represented by a bead-spring model where the molecu-
lar weight of each block was converted to degree of poly-
merization with a correction to account for differences in
repeat unit volumes. These volumes of 69 3 and 138 3 for
PDMS68 and PEO,69 respectively, were scaled to the reference
volume for LTA of 108 , calculated by ChemAxon.70 The vol-
ume ratios of PDMS and PEO to LTA were then used to cal-
culate the corresponding numbers of beads to represent a
PDMS-b-PEO chain at each molecular weight. For example,
we used 21 and 33 beads for D1.1O2.1 and 21 and 30 beads
for D1.1O1.9.
Selective Binding Leading to Stronger Segregation and
Increasing TODT
To quantify the increased phase separation behavior of
PDMS-b-PEO in the presence of LTA, we quantitatively com-
pared the FloryHuggins parameters of neat BCPs to blends
of BCPs with LTA. Initially the v parameters of neat PDMS-b-
PEO were obtained by analysis of SAXS profiles in the disor-
dered phase at various temperatures. The analysis was based
on Leiblers mean field theory14 and modified to account for
the polydispersity and asymmetry of the block copoly-
mers.71,72 To ensure accessibility of the temperature window
of the disordered state and reliability of the calculations, the
two lowest molecular weight BCPsD1.1O1.9 and D1.1O2.1
with low order-disorder transition temperatures (TODT 5 80
8C, see Supporting Information Figs. S3 and S4) were sub-
jected to this analysis. Four parameters, including the statis-
tical segment lengths of both polymers (bEO, bDMS) and
fitting constants K and v, were optimized to fit the SAXS pat-
tern at a particular temperature. The data analysis is sum-
marized in Supporting Information Figure S5. Both polymers
have similar FloryHuggins parameters (v (D1.1O1.9) 5 16.4/
T 1 0.17 and v (D1.1O2.1) 5 22.8/T 1 0.15) as shown on
Figure 5. These values are significantly higher than the v val-
ues of both PS-b-PMMA and PDMS-b-PS, and slightly higher
than for PDMS-b-PMMA (Table 2) suggesting that PDMS-b-
PEO could achieve smaller, nanoscale features.
Shifting attention to the LTA blends, the effective v parame-
ters, veff, of PDMS-b-PEO/LTA could not be obtained by the
same method used for neat PDMS-b-PEO. Considering the
onset decomposition temperature of LTA, 150 8C,41 the dis-
ordered phase temperature windows of these blends for veff
analysis would be higher than the LTA decomposition tem-
perature. Therefore, a theoretical model was used to
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TABLE 2 FloryHuggins Parameters of Selected Block

Copolymers

Sample va v at 150 8C
35
PS-b-PMMA 4.46/T10.028 0.039
PDMS-b-PS49 6.85/T10.072 0.088
49
PDMS-b-PMMA 24.4/T10.13 0.188
PDMS-b-PEO 16.4/T 1 0.17 0.208

a
FloryHuggins parameters were obtained by analyzing disordered
SAXS profiles based on Leiblers random phase approximation.14 The
reference volume for each case is 0.1 nm3.

quantitatively evaluate veff of the PDMS-b-PEO/LTA blends.

The random phase approximation (RPA)14 applied to a FIGURE 4 The TODT curves as a function of the volume ratio of
supramolecular bead spring model allowed us to predict the LTA additive for two PDMS-b-PEO samples. Scattered points
increase in TODT resulting from addition of LTA. The spinodal are drawn from experiments with D1.1O2.1 (circle) and D1.1O1.9
phase boundary (the stability limit of the homogeneous dis- (square), and lines are from the RPA modeling using 2130
ordered phase) can be calculated by solving equation C.1 beads (dashed) and 2133 beads (solid).
(see Supporting Information). The order-disorder transition
ture of LTA.73 Using the best fit parameters, the RPA analysis
temperatures, TODTs, are fit assuming a temperature depend-
predicts that approximately 80% of inserted LTAs are hydro-
ence of the various v parameters of the form v 5 a/T 1 b.
gen bonded to the PEO block of D1.1O2.1 at 140 8C, according
The two parameters characterizing vAB (PDMS, PEO) were deter-
to Keq calculations (see Supporting Information Fig. S6).
mined using the neat block copolymer experimental data.
vBC (PEO, LTA), vBD (PEO, PEO/LTA), vCD (LTA, PEO/LTA) were set to From fitting the a and b variables in the v parameter expres-
zero, assuming that the EO segments are mostly consumed by sion, we were able to predict the effective interaction param-
hydrogen bonding to produce a supramolecular PEO/LTA eter of the block copolymer-LTA blends. Previously, the v for
block which is compatible with LTA. The four a and b parame- PDMS-b-PEO without LTA was measured to be 16.44/
ters contained in vAC (PDMS, LTA) and vAD (PDMS, PEO/LTA) were T 1 0.169 for D1.1O1.9 and 22.8/T 1 0.148 for D1.1O2.1. Figure
the only unknown variables to appear in the RPA equations 5 shows that the anticipated increase in v when LTA was
and were matched with experimental datasets obtained from added to the block copolymers was correct. Fitting the TODT
D1.1O2.1 and D1.1O1.9. For vAD (PDMS, PEO/LTA), the effective curves from the RPA-based field-theoretic modeling to the
FloryHuggins parameter was expected to be larger than that
of the bare block copolymer, vAB (PDMS, PEO), due to an unfavor-
able interaction between the bound LTA and PDMS segments.
For our study, the fitting to the RPA expressions is difficult
because of the limited data on TODT from the two low molecu-
lar weight samples below the thermal decomposition limit of
LTA.73 To improve the statistical significance of the fitted
parameters, we assumed that vAC (PDMS, LTA) and vAD (PDMS,
PEO/LTA) are the same, that is, free and bound LTA interact
with PDMS segments similarly. Thus, a single a and b pair
were the only two fitting parameters for the D1.1O1.9 and
D1.1O2.1 analysis.

Improved Phase Separation Shifts TODT

As shown in Figure 4, TODT curves derived from the RPA
modeling were obtained by fitting to the corresponding
experimental data by adjusting a and b of vAC (PDMS, LTA) and
vAD (PDMS, PEO/LTA) iteratively. The close match between calcu-
lated results and experimental observations demonstrate a
simple trend: as the amount of LTA added to PDMS-b-PEO
was increased, the ODT increases nearly linearly and then
flattens as LTA binding sites on the PEO backbone begin to
saturate. The RPA modeling was terminated at 10.5% LTA
for D1.1O1.9 and 15.0% for D1.1O2.1 because at these incorpo-
rations, the TODT moves above the decomposition tempera-
FIGURE 5 The FloryHuggins parameter, v, as a function of the
temperature. The experimentally measured v of PDMS-b-PEO
from two samples D1.1O2.1 (blue) and D1.1O1.9 (red) are plotted
as dashed lines with data points (lower pair) and the derived v
of PDMS-b-(PEO/LTA) by RPA are plotted as solid lines (upper
pair). The derived v from the higher volume fraction of PEO
(D1.1O2.1) increases from the original v of PDMS-b-PEO more
than the smaller volume fraction of PEO (D1.1O1.9). [Color figure
can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]

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ARTICLE WWW.POLYMERCHEMISTRY.ORG
experimental data shows that the effective v, both vAD (PDMS,
PEO/LTA) and vAC (PDMS, LTA), between PDMS and the PEO/LTA
suprablock increased from 16.44/T 1 0.169 to 57.0/T 1 0.23
for D1.1O1.9 and from 22.8/T 1 0.148 to 75.0/T 1 0.26 for
D1.1O2.1. The difference between the extracted v expressions
for the two PDMS-b-(PEO/LTA) samples is likely due to the dif-
ferences in the bare v parameters of the pure PDMS-b-PEO
copolymers and the different volume fractions of PEO that par-
ticipate in H-bonding. The temperature dependence of the
effective v is much higher after LTA binding, suggesting a large
unfavorable enthalpic interaction between bound (or free) LTA
and PDMS. The increase in effective v from vAB (PDMS, PEO) to
vAD (PDMS, PEO/LTA) is approximately equivalent to 0.36-0.43 at
room temperature with the overall increase of vAD (PDMS, PEO/
LTA) being  80120% (see Figure 5). This relatively large
effective v parameter excludes LTA from the PDMS domains
and enhances binding to PEO. When LTA binds exclusively to
PEO, the resulting PEO/LTA supramolecular block copolymer
is more polar than PEO alone, as depicted in Figure 1 with the
supramolecular assembly resulting in an increased PDMS-b-
(PEO/LTA) v. Significantly, these theoretical calculations predict
a shift towards higher v values, which would improve phase
separation and self-assembly. Experiments were able to further
corroborate this finding: in the pure D1.7O2.0 case at 60 8C,
only the principal scattering peak was observed, indicating
ordered domains without long-range ordering. On addition of
LTA, higher order SAXS reflections (nq* 5 1:2:3) become appa-
rent, confirming our hypothesis that LTA enhances the self-
assembly capabilities of PDMS-b-PEO and allows for tuning of
phase separation, effective molar volume and domain period.
As the amount of LTA was increased in D1.7O2.0, the morphol-
ogy gradually evolved from lamellae (5%  20 wt % LTA) to
cylinders (25 wt % LTA), as pindicated
p by the characteristic
peaks position at ratios q*: 3q*: 7q* (see Fig. 3). Similarly,
as the amount of LTA was increased for D1.1O2.1, D2.2O5.0 and
D9.0O1.8, the morphology changed from lamella (<5%) to
gyroid (>20%), from lamella (<10%) to hexagonal cylinder
(>25%), and from bcc sphere (<2%) to hexagonal cylinder
(>5%), respectively (Supporting Information Figs. S7S9). If
we assume homogeneous LTA binding to PEO for all PDMS-
b-PEO compositions, the model calculations indicate that the
volume fractions of PDMS can be decreased from f 5 0.5,
0.38, 0.34, and 0.86 without LTA to feff 5 0.42, 0.32, 0.29,
and 0.73, respectively, upon 30 wt % incorporation of LTA
without causing a morphological change in the PDMS-b-PEO/
LTA blend in the D1.7O2.0, D1.1O2.1, D2.2O5.0, and D9.0O1.8 sam-
ples. The addition of LTA consequently not only allows us to
improve phase separation and change domain periods, but
also alters the thermodynamically most stable morphology at
a given temperature, which allows accessibility of different
morphologies through the same block copolymer.
CONCLUSIONS
The influence of (L)-tartaric acid (LTA) on the assembly of a
library of PDMS-b-PEO block copolymers (BCPs) with differ-
ent molecular weights and volume fractions was examined.
2206 JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2016, 54, 22002208
JOURNAL OF
POLYMER SCIENCE
The specific H-bonding, supramolecular assembly of LTA
with the PEO domains of the block copolymer decreased the
PEO blocks tendency toward crystallization and improved
phase separation. This supramolecular driven assembly was
modeled via the random phase approximation (RPA) utilizing
a bead-spring model with the model predictions, obtained
from fits to experimental TODT data, suggesting a large effec-
tive v for PDMS and LTA, which drives LTA into the PEO
domains and enhances hydrogen bonding of LTA to PEO. The
increased polarity of the PEO/LTA supra-block is quantified
by a predicted 100% increase in v for PDMS-b-PEO/LTA over
PDMS-b-PEO, and the order-disorder transition temperature
is observed both experimentally and theoretically to be a
monotonically increasing function of LTA concentration. The
higher volume PEO/LTA supra-blocks, further swollen with
free LTA can further drive a sequence of morphological tran-
sitions, consistent with SAXS analysis of the blends. These
block copolymers achieved lamellar domain periods as low
as 7.9 nm and show promise for next generation block
copolymer lithographic systems.
ACKNOWLEDGMENTS
We thank The Dow Chemical Company through the Dow Mate-
rial Institute in UCSB and the PREM program of the National
Science Foundation (DMR-1205194) for financial support. The
following Dow researchers are thanked for insightful discus-
sions Phillip Hustad, Matthew Christianson, John Kramer,
Bryan Barton and Paul Clark (DOW). Project assistance by
Hazel Sprafke (UCSB) and insightful discussion with Weichao
Shi, Brian Stahl and Nicolas Treat (UCSB) are gratefully
acknowledged. The computer simulations presented in this
work were performed using computational facilities at the Cali-
fornia NanoSystems Institute (CNSI) and Materials Research
Laboratory (MRL) at the University of California, Santa Barbara.
The MRL Central Facilities are supported by the MRSEC Pro-
gram of the NSF under Award No. DMR 1121053; a member of
the NSF-funded Materials Research Facilities Network
(www.mrfn.org). C.W.P. acknowledges the Alexander von Hum-
bolt foundation for financial support.
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