Directing The Self-Assembly of Block Copolymers

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Prog. Polym. Sci. 32 (2007) 11521204

www.elsevier.com/locate/ppolysci
Directing the self-assembly of block copolymers

S.B. Darling
Center for Nanoscale Materials, Argonne National Laboratory, Argonne 60439, USA
Received 26 January 2007; received in revised form 26 March 2007; accepted 14 May 2007
Available online 2 June 2007
Abstract
Recently, a new spotlight has been focused on block copolymers, thoroughly studied for nearly half a century, because
of their potential use in numerous nanotechnologies. This renewed interest is a consequence of the self-assembled
microdomains characteristic of these materials. The size, shape, and arrangement of these nanoscopic structures are all
tunable through synthetic chemistry of the constituent molecules. Capturing the vast technological potential of block
copolymers will, in many cases, require precise control over the orientation and alignment of the microdomains. This
review summarizes extant applications and alignment techniques and provides an outlook toward the future. In an effort
to provide a practical resource for researchers, the article is structured to identify the reported alignment approaches for a
given polymer morphology rather than sorting by alignment technique. Specic materials have also been deemphasized
because the alignment methods, with few exceptions, are general to a specic morphology or set of morphologies. In
addition to a detailed summary of traditional methodologies, some very recent results such as optical alignment of liquid
crystalline block copolymers, lithographic chemical patterning, and alignment in pores are highlighted.
r 2007 Elsevier Ltd. All rights reserved.
Keywords: Block copolymers; Nanostructures; Nanomaterials; Directed self-assembly; Graphoepitaxy; Alignment
Contents
1. Introduction to block copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1153

2. Block copolymers for technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1154
2.1. Masks and pores. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1154
2.2. Nanoparticle synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1156
2.3. Nanomaterial templating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1158
3. Defect evolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1161
4. Guiding assembly in the bulk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1164
4.1. Spherical phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1165
4.2. Cylindrical phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1165
4.3. Lamellar phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1167
4.4. Other phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1172
5. Guiding assembly in thin lms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1172
Tel.: +1 630 252 4580; fax: +630 252 4646.

E-mail address: darling@anl.gov
0079-6700/$ - see front matter r 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2007.05.004
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S.B. Darling / Prog. Polym. Sci. 32 (2007) 11521204 1153
5.1. Spherical phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1173

5.2. Cylindrical phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1174
5.2.1. Oriented parallel to the substrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1175
5.2.2. Oriented perpendicular to the substrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1180
5.2.3. Lamellar phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1183
6. Guiding assembly by three-dimensional connement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1188
7. Conclusions and challenges for the future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1191
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1192
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1192
1. Introduction to block copolymers another [4], but this review will focus largely on
the simplest and most studied categorythe AB
Soft materials, which have characteristic uidlike diblock composed of a linear chain of type A
disorder on short length scales and high order at monomers bound on one end to a linear chain of
longer length scales, are increasingly drawing the type B monomers.
attention of both scientists and engineers. These Thermodynamic incompatibility between the A
materials, including colloids, surfactants, mem- and B blocks drives a collection of AB diblock
branes, biomaterials, polymers, and their compo- molecules to self-organize via microphase separa-
sites, are easily deformable by external stresses and tion in which the contact between similar and
often display non-equilibrium behavior. Much of dissimilar blocks are maximized and minimized,
the interest in soft matter derives from the inherent respectively. Macrophase separation is prevented by
capacity for many of these materials to self- the entropic forces stemming from the covalent
assemble into nanostructures. Self-organization is bonds holding the A and B blocks together. The
a powerful means to fabricate useful mesostructured system, then, must reach a compromise between
materials and is recurrently employed in natural mixing and separating. The temperature-dependent
systems [1]. From a technological perspective, self- FloryHuggins interaction parameter, wAB, de-
assembly is low-cost, fast, and easily scalable. Self- scribes the free energy cost of contact between
assembling systems also capture the interest of dissimilar monomers that governs this process [5].
fundamental researchers because they are governed Two additional parameters that determine the
by a fascinating interplay between weak forces. ultimate morphology of the microphase system are
Block copolymers (BCPs) are composed of two or the degree of polymerization, N, and the relative
more chemically distinct, and frequently immiscible, composition fractions, fA and fB, where fA NA/N
polymer blocks covalently bound together. The and fA+fB 1 [6]. Common periodic phases for
complex structure of BCP materials leads to a AB diblocks, with increasing fA, include body-
variety of useful properties; indeed, industrial centered cubic A spheres in a B matrix, hexagonally
applications for BCPs in thermoplastic elastomers, packed A cylinders in a B matrix, bicontinuous
foams, adhesives, etc. have been around for gyroid, and lamellae. Fig. 1 depicts these morphol-
decades. Recently, renewed attention has been ogies with the diblock molecules represented as
directed at these materials for applications in high- simplied two-color chains. Several additional
technology. Modern synthetic chemistry enables the phases are observed experimentally, but are not
tailoring of the structure, and hence the properties, thermodynamically stable [4]. This discussion as-
of both the individual blocks and the ensemble. sumes ideal morphologies whereas, generally, the
Mechanical, mass transport, electrical, and optical synthesis of BCPs is subject to kinetic constraints
behavior in the solid state are all tunable in this way that result in a distribution of molecular weights
if one pays careful attention to the molecular and typically some degree of structural heterogene-
architecture. While BCP solutions have also gener- ity. Theoretical treatments [710], supported by
ated signicant interest, in particular in the context some experiments [1113], suggest that polydisper-
of micelles for drug delivery and other medical sity leads to shifting phase boundaries and to an
applications [2,3], this review will only address solid- increase in the domain spacing because the existence
state behavior and applications. There are myriad of different chain lengths in a polydisperse system
ways in which blocks can be attached to one lowers the stretching energy [10]. Interestingly, these
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1154 S.B. Darling / Prog. Polym. Sci. 32 (2007) 11521204
Fig. 1. Schematics of thermodynamically stable diblock copolymer phases. The AB diblock copolymer, such as the PS-b-PMMA
molecule represented at the top, is depicted as a simple two-color chain for simplicity. The chains self-organize such that contact between
the immiscible blocks is minimized, with the structure determined primarily by the relative lengths of the two polymer blocks (fA).
studies have shown that polydispersity leads BCPs to the tunability of the size, shape, and composi-
to order more readily, but a complete removal of tion of diblock copolymers, they are attractive
defects over macroscopic length scales requires for a number of nanotechnologies. A brief summary
extensive top-down guidance. of recent applications will be discussed here, but
more detailed information is available in the
literature [1416].
2. Block copolymers for technology
Nanotechnology hinges on the ability to create 2.1. Masks and pores

precisely ordered nanoscale structures. Traditionally,
nanostructures have been dened using top-down The semiconductor and magnetic recording in-
lithographic techniques based on electromagnetic dustries have depended on the exponential growth
radiation, energetic particle beams, and scanning of device densities for many years. As this trend
probe microscopes. Top-down methods are subject continues into the future, traditional fabrication
to several intrinsic limitations to their practical methodologies will rapidly become prohibitively
efcacy. Diffraction depth of focus, electrostatic expensive. Self-assembling nanoscale materials such
interactions, and serial patterning are typical draw- as BCPs may be able to transcend these limitations
backs of these approaches that result in both [17]. Nanoscale structural periodicity together with
expensive facilities and slow pattern writing. Owing differential etch resistance of the polymer blocks is a
ARTICLE IN PRESS
potentially powerful combination for next-genera- Fig. 2 illustrates how arrays of nanoscopic inorganic
tion lithographic technology [18,19]. The rst features can be fabricated starting with a PS-b-PFS
demonstration of BCP lms as lithographic masks BCP lm as a lithographic mask. The majority of
was reported by Mansky et al., where they used BCP lithography studies have focused on the
poly(styrene-block-butadiene) (PS-b-PB) diblocks spherical morphology, though there have been some
[20,21]. Ober et al. extended this approach to notable investigations of 1-D structures derived
negative tone resists by using hydrosiloxane-mod- from cylindrical BCPs [35,38,39].
ied poly(diene) blocks and were able to generate Subtly different from masking, pore lling is
patterns with 100 nm resolution [22]. Feature another method for nanopatterning with BCPs. In
densities on the order of 1011/cm2, with model this technique, either spherical phase lms or
structures having characteristic length scales rival- vertically oriented cylindrical lms are modied
ing state-of-the-art electron beam lithography, have with physical or chemical treatment to remove the
been reported [2325]. One of the drawbacks of minority block [4044]. Rather than using the
these approaches is the relatively weak differential remaining array of holes as a lithographic mask,
etch contrast between the two blocks. Greater etch they can be directly lled with a functional material
contrast can be achieved either by selectively with the advantage of structural stability provided
loading one of the blocks with inorganic material by the majority block matrix, which is often
[23,26,27], as is commonly done to improve imaging strengthened by crosslinking during the removal of
contrast in electron microscopy, or by replacing one the minority block. Alternatively, the pore array
of the blocks with inorganic or organometallic itself can serve as an ensemble of nanoelectrodes for
moieties. A popular option is poly(styrene-block- sensitive, rapid-response sensors [45]. Capillary
ferrocenyldimethylsilane) (PS-b-PFS) BCPs [2837], forces are typically relied upon to ll the template
which have the added advantage that the PFS block pores, but electrophoretic deposition has also
can serve as a precursor for magnetic ceramics. been proven effective [46]. Filling pores with
Fig. 2. Tilted SEM images of subsequent structures prepared via block copolymer lithography. (a) An etched PS-b-PFS block copolymer
lm on a multilayer substrate. (b) Silicon oxide pillars capped with PFS on a tungsten and cobalt lm. (c) Tungsten dots on cobalt lm. (d)
Tungsten-capped cobalt nanodots array. (Reproduced with permission from Cheng et al. Adv Mater (2001) Wiley-VCH [31].)
ARTICLE IN PRESS
ferromagnetic material, particularly for cylindrical tions, have been produced within porous poly(styr-
pores that have the benet of shape anisotropy, ene-block-2-vinylpyridine) (PS-b-PVP) layers [59],
results in a material with potential application in and protein nanoarrays for biosensors have been
ultrahigh-density magnetic recording [4749]. A generated using poly(styrene-block-methylmethacry-
phenomenological illustration of this approach is late) (PS-b-PMMA) [60].
depicted in Fig. 3. Etched cylindrical domains A variation on the pore-lling technique is to use
oriented parallel to the surface can also be lled the porous BCP itself, either in thin lms or in the
with magnetic nanomaterials [50], though the ad- bulk [61], as a functional material, for example as a
sorption mechanism is qualitatively different [51]. nanostructured membrane. These materials have
Metal-oxide-semiconductor (MOS) arrays based on advantages over conventional surfactant routes
BCP templates show promise for low voltage because the 550 nm pore sizes are larger, thereby
memory devices and decoupling capacitors in sig- permitting a wider variety of materials to permeate
nal-of-interest (SOI) circuits [5256], while semicon- the network. This procedure is sometimes confused
ductor nanopillar structures have advantages for with the fabrication of honeycomb porous materials
photovoltaics [57]. Mechanical applications are also via controlled water condensation on BCP lms,
accessible such as in the patterning of elastomers though this practice is not directly templated by the
using BCP porous templates [58], although these polymer domains and produces pores 41 mm in
efforts are hampered by poor wetting behavior of the diameter [62]. The rst realization of the direct
elastomer precursor on the PS matrix. Organic and templating approach, in which the nanoscopic
biomaterials can also be grown in the pores of channels were also coated with nickel to create a
modied diblock lms. Films of polyaniline, a nanohybrid for catalytic reactor use, was reported
conducting polymer with possible sensor applica- by Hashimoto et al. [63]. Driven by demands for
low dielectric constant materials in the microelec-
tronics industry and by molecular sieve applica-
tions, many groups have used BCPs to fabricate
nanostructured silica ceramics [6471]. Recently,
researchers have pushed toward production of
monolithic samples with macroscopic total pore
volumes using the gyroid morphology [72], toward
diblock systems in which one of the blocks is easily
removed by selective dissolution [73], and toward
additional applications such as antireection coat-
ings [74]. A micrograph showing the nanoporosity
achievable with this approach is shown in Fig. 4.
This image is from a fractured monolith of a
poly(styrene-block-lactide) (PS-b-PLA) that has
been treated with chemical etchant to selectively
remove the PLA domains.
2.2. Nanoparticle synthesis
Domains within BCPs can be used as spatially

localized synthetic vessels for the growth of
nanoparticles. A review of this subject by Cohen
[75] is available, and some more recent results have
Fig. 3. Schematic of high-density nanowire fabrication in a been summarized elsewhere [15]. Synthesis is typi-
polymer matrix. (a) An asymmetric diblock copolymer annealed cally achieved by loading pre-formed BCP domains
above Tg under an applied electric eld, forming a hexagonal with inorganic precursors that are subsequently
array of cylinders oriented normal to the lm surface. (b) After
reduced, although one can alternatively sequester
removal of the minor component, a nanoporous lm is formed.
(c) By electrodeposition, nanowires can be grown in the porous the inorganic material to the polymer prior to phase
template. (Reproduced with permission from Thurn-Albrecht segregationperhaps even covalently building it
et al. Science (2000) AAAS [47].) into one of the blocks. Using the latter approach,
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PbS, Pd, and Pt clusters have been fabricated a variety of metal and semiconductor nanoparticles
[7678] as have nanostructured ceramic materials [8086]. A recent example of this approach is
[79]. Synthesis of organometallic BCPs is complex, depicted in Fig. 5, where metal was incorporated
so the former method is generally preferred. into the PS block of a PS-b-PMMA lamellar material
Selective loading has been widely applied to create thereby growing ordered arrays of nanoparticles. The
spherical morphology is most commonly used, but
cylindrical domains offer a platform to compete with
anodic aluminum oxide [87], with lamellar BCPs
multilayered nanocomposites can be made without
invoking layer-by-layer processing [8890], and
recently a group has grown Pd nanoparticles within
the pore network created by selective removal of one
block in a gyroid BCP [91]. It is also possible to
create polymerceramic hybrids using similar ap-
proaches; there is a review of this burgeoning area
highlighting the breadth of accessible morphologies
[92]. Because of their interesting magnetic properties
and their applicability to ultrahigh density magnetic
recording, monodispersed, ferromagnetic nanoparti-
cles and magnetic ceramics are of great interest. BCP
nanoreactors have recently been utilized toward this
end [9397]. Titania nanoparticles are also a desired
target for use in catalysis, energy conversion, and
sunscreens. Several groups have demonstrated BCP
templated synthesis of TiO2 particles [98102], as well
as the related synthesis of silica mesostructures
[100,103]. Fabrication of a wider variety of materials
can be achieved by using selectively loaded BCP
Fig. 4. SEM image from a fractured surface of an aligned materials as patterned catalysts. This approach has
nanochannel array fabricated by selectively removing one block
from a PS-b-PLA diblock copolymer with gyroid morphology. been employed with gold and iron oxide to grow
(Reproduced with permission from Mao et al. Soft Matter (2006) ZnO nanowhiskers [104] and carbon nanotubes
The Royal Society of Chemistry [72].) [105107], respectively.
Fig. 5. TEM images of cross sections of lamellar PS-b-PMMA that was exposed to Pd(acac)2 vapor. Pd nanoparticles are observed to
selectively grow within the PS layers resulting in a nanoscale ordered array of particles separated by organic sheets. (Reproduced with
permission from Horiuchi et al. Langmuir (2003) American Chemical Society [85].)
ARTICLE IN PRESS
2.3. Nanomaterial templating segregate to the boundaries between the BCP

domains. This has been achieved using Au and
Rather than directly synthesizing materials within SiO2 nanoparticles in lamellar poly(styrene-block-
BCP domains, one can also use the periodic ethylene-alt-propylene) (PS-b-PEP) (Fig. 6) [113]. In
chemistry of a BCP to template the adsorption or this system, the long-chain thiol-capped Au parti-
absorption of various nanomaterials to form a cles migrated to the junctions between the blocks
complex composite. This can be achieved either by and the short-chain trimethylsilane-capped SiO2
depositing material on pre-formed BCP lms or by particles absorbed in the center of the PEP domains.
codepositing the material and the BCP. Bockstaller Chemistry of the capping molecules can be adjusted
et al. and Balazs et al. have recently provided to engineer the ultimate structure [114]. Chemistry,
thorough reviews of BCP nanocomposites [108,109], however, is not the only factor that determines
so only a synopsis of the salient results with further nanoparticle location in BCPs. Particle size, even for
topical experiments published following these re- slight changes, can also play a signicant role [115].
views will be discussed here. Casting solvent can also have a substantial impact
The most widespread application of BCP tem- on the eventual morphology when the particle
plating is that of colloidal nanoparticles. Thomas binding contrast between the two blocks is small
and coworkers were among the original developers [116]. Self-consistent eld (SCF) theory for poly-
of the codeposition methodology [110,111]. In this mers has been combined with density functional
work, surfactant-mediated CdSe and core-shell theory for nanoparticles to develop a predictive
(CdSe)ZnS nanoparticles were mixed with diblock model for the morphology and thermodynamic
copolymers containing a phosphine-modied block properties of BCP-particle composites [117119].
that preferentially sequestered the inorganic clus- Interestingly, these studies present entirely new
ters. Similar results have recently been reported mesophase structures for the hybrid materials in
using unmodied PS-b-PVP [112]. An interesting which the particles can form useful one- and two-
twist on this approach is to create ternary systems dimensional (1- and 2-D) assemblies. Neutron
by driving one set of particles to sequester within a scattering has been employed to investigate such
polymer block and a second set of particles to hybrids and has determined that when nanoparticles
Fig. 6. Bright eld electron image of microtomed lamellar PS-b-PEP loaded with both gold and silicon oxide nanoparticles, which
selectively reside at the block junctions and within the PEP domains, respectively. The inset contains a schematic of the particle locations.
(Reproduced with permission from Bockstaller et al. J Am Chem Soc (2003) American Chemical Society [113].)
ARTICLE IN PRESS
are selectively sequestered in one domain they swell acid-capped FePt nanoparticles are observed to
that domain and increase the interfacial curvature reside preferentially within the nanoscale regions
[120]. Incorporation of nanoparticles can also affect from which PMMA cylinders were removed. In this
the orientation of BCP domains, for example case, it is forces associated with the spin-casting
causing cylindrical domains to orient perpendicular process itself that produce the selective adsorption.
to a non-neutral substrate [121]. It has also been There are also instances of nanoscale roughness
shown that, inverting the conceptual approach, one leading to self-organization of colloidal particles
can rely on self-assembly to form BCP micellar following drop casting. In these cases, surface
shells around functional nanoparticles to create, for tension is the driving force [129].
example, encapsulated magnetic nanostructures For applications in which nanostructured pure
[122]. metal, that is, metal that is not coated with organic
Rather that incorporate nanoparticles into the molecules, is needed, there are several options
bulk phase of a BCP, some applications, such as available with block copolymer templating. Pore
catalysis and magnetic recording, necessitate a lling and templating of nanoparticles are two
surface presentation for the nanoparticles. For this approaches already discussed, but an additional,
approach, it is critical that the BCP present multiple simpler method is available. For some metal/
blocks at or near the free interface. PS-b-PMMA, polymer systems, simply evaporating metal onto a
which has both PS and PMMA domains displayed phase-separated BCP lm will result in selective
at the surface at appropriate surface thickness, is decoration of one of the blocks. Jaeger et al. have
frequently utilized for this reason [123]. Zehner et al.
pioneered this approach with Au and Pd nanopar-
ticles on a PS-b-PMMA lm [124,125]. The capping
molecules included alkanethiols, arenethiols, and
tetraalkylammonium, all of which preferentially
bound to the PS phase due to the common
hydrophobic molecular tails. These authors further
showed that a wider variety of composite materials
was available through the integration of an addi-
tional processing stage. The passivated Pd colloids
were used as a catalyst for electroless copper plating
with nanoscale structural precision [125]. This
approach produced 1-D clusters of Cu, though the
structures contained many voids and hence were not
suitable for nanowire applications. Alternatively,
one can use post-treatment with oxygen plasma to
induce aggregation of selectively adsorbed metallic
nanoparticles to produce continuous, conductive
nanowires [126]. Hydrophobic or hydrophilic inter-
actions typically drive the selective adsorption of
colloids on BCP lms [124,125,127], but other,
potentially more robust, forces can be used as well.
Hydrogen bonding has the advantage of high
specicity and has been proven effective at control-
ling nanoparticle adsorption on BCP lms [128].
Another approach is to utilize physical, rather than
chemical, forces to guide the self-assembly process.
Cylindrical phase PS-b-PMMA lms modied with
VUV light to remove the surface PMMA domains
Fig. 7. AFM micrograph showing very high selectivity adsorp-
have been demonstrated as highly selective scaffolds
tion of FePt nanoparticles on a UV-modied cylindrical PS-b-
for nanoparticle adsorption that is independent of PMMA lm at (a) low and (b) high coverage. (Reproduced with
the chemistry of the surfactant capping molecules permission from Darling et al. Adv Mater (2005) Wiley-VCH
[50,51]. This system is depicted in Fig. 7, where oleic [50].)
ARTICLE IN PRESS
performed a series of experiments, beginning with non-equilibrium structures. Selectivity can be ratio-
Au decoration of PS-b-PMMA and PS-b-PVP lms nalized with a diffusive mobility contrast between
[130]. This work was followed by several papers the two polymer blocks, as supported by Monte
reporting successful templating for various metallic Carlo simulations [132]. Taking advantage of this
elements, with noble metals decorating the PS phase mechanism, one can begin to manipulate the
and others decorating the PMMA phase [131,132]. diblock chemistries, and hence the diffusion proper-
Fig. 8 illustrates the selective adsorption of Au and ties, to tune the selectivity of desired materials. One
Ag onto the PS domains, forming arrays of such approach is to use low doses of high-energy
nanoscale clusters and wires. Similar results have electrons to locally crosslink or degrade specic
also been obtained using cylindrical triblock copo- blocks, thereby inuencing the diffusivity of subse-
lymer thin lm templates onto which silver clusters quently adsorbed metals [134].
were soft-landed [133]. Even at high metal loading Controlled positioning of biomolecules with high
fractions, the metals tend to form nanoclusters and areal density on surfaces is an essential aspect of
do not aggregate into wires, with the exception of basic cell biology research and of applied research
large Ag thicknesses. Realizing that the metal involving combinatorial screening, proteomic ar-
surface tension prefers a spherical shape, the rays, and biosensors. While many lithographic
observed tendency toward cluster formation is not techniques have been applied to this end, these
surprising. Indeed, the silver nanowires are highly methods tend to suffer from the usual limitations
Fig. 8. TEM micrographs of (a) aggregation of Au metal, vapor-deposited onto copolymer lm prior to annealing. (b) Annealing
produces highly selective Au decoration of the PS domains. (c) Repeated deposition and short-time annealing leads to densely packed
nanochains. (d) and (e) Ag nanowires deposited onto the copolymer lm without subsequent annealing leads to self-assembled nanowires
on the PS domains. Scale bars: 200 nm in (ac), and 100 nm in (d and e). (Reproduced with permission from Lopes et al. Nature (2001)
Macmillan Publishers Ltd [131]).
ARTICLE IN PRESS
associated with top-down lithography: resolution

and serial processing. It has recently been demon-
strated that BCP lms can effectively immobilize
protein molecules on surfaces on the nanometer
scale [135]. In this work, model proteins displayed a
preferential interaction with the PS phase of a PS-b-
PMMA thin lm. Subsequent studies with X-ray
photoemission electron microscopy have established
that the adsorption location is inuenced both by
the concentration of the protein solution and by the
exposure time [136]. The observed dependence
indicates that solvated/adsorbed protein equili-
brium is established more rapidly with PS than
with PMMA. Alternative adsorption mechanisms
can also be utilized to create polymerbiomolecule
hybrid nanostructureseven using the same BCP
template. Molecular combing, in which a receding
contact line can stretch and align linear molecules
on surfaces, has been applied to DNA adsorption
on a PS-b-PMMA lm [137]. The structured three- Fig. 9. AFM image showing the collecting effect of the molecular
phase contact line that is generated by an aqueous combing process on a PS-b-PMMA lm in which DNA molecules
solution interacting with both polymer blocks leads are aligned on the surface. The arrow denotes the direction of the
moving contact line. The image is 1.5 1.5 mm. (Reproduced with
to nanoscale structuring of the drying meniscus. permission from Liu et al. Langmuir (2006) American Chemical
Dynamic lateral forces produced by this process Society [137].)
direct DNA molecules into aligned geometries
(Fig. 9).
3. Defect evolution
The previous section highlights the vast potential

of BCPs for nanotechnological applications. While
some functions can be satisfactorily addressed
simply with the local nanoscale self-assembled
structure of BCPs, the principal limitation to those
applications that require long-range order is that
BCPs do not inherently display global ordering.
Rather, domains of locally ordered periodicity tend
to nucleate randomly ultimately producing a
material with many grains of random orientation.
Fig. 10 depicts a typical atomic force microscopy
(AFM) image in which a cylinder-forming PS-b-
PMMA thin lm displays orientational order only
over several lattice constants with numerous topo-
logical defects. The topology of defects in BCPs is
analogous to that in liquid crystals, so the nomen-
Fig. 10. Tapping-mode AFM micrograph of a typical cylinder-
clature classifying them is similar [138]. Edge forming PS-b-PMMA thin lm. The polymer domains are aligned
dislocations are a common defect observed in over a length scale corresponding to several periods, but there is
diblock copolymers. One can describe a dislocation no long-range order.
(+ or ) by determining the change in the director
rotation around the dislocation core. Directors can appear as pairs with opposite sign. Fig. 11 depicts
display inclination discontinuities that result in examples of common topological defects in BCP
disclinations (12 or 12). Disclinations frequently lms. Thermodynamically, all of these defects are
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unstable, but BCP systems become kinetically the annihilation of disclination pairs through the
trapped due to their relatively low mobility. action of dislocations. Disclination pairs are sepa-
Thermal annealing above the polymer glass transi- rated by several domains, so domains must be
tion temperature (Tg), where mobility is amplied, removed as the disclination lines annihilate. The
will drive many defects to propagate and annihilate. mechanism for this process was identied as motion
Motivated by both technological and fundamental of dislocation loops, either in the domain direction
factors, several groups have studied the structural (climb) or transverse to the domain direction
evolution of these defects in detail. (glide) [142].
Early studies of BCP defect evolution largely Electron microscopy techniques can provide
relied on techniques such as optical birefringence complementary local information [145147] but at
[139], neutron reection [140], small angle X-ray the expense of beam-induced damage that prohibits
scattering (SAXS) [141,142], and depolarized light observation of structural dynamics. AFM, on the
scattering [143] to ascertain the spatially averaged other hand, is capable of non-destructive imaging
behavior of the ensemble of defects. These and has been used productively to probe defect
experiments revealed that the mobility and interac- evolution in diblock copolymer thin lms [148153].
tions of different defect types is a function of The polymer systems examined in these experiments
the interplay of forces driving the propagation were 2-D, thereby constraining the topological
and annihilation processes. Some theories that evolution more so than in 3-D systems. These
delve into this interaction, focusing on bulk BCP studies conrm that the dominant route for
systems, are reviewed by Fredrickson and Bates increasing the long-range order, sometimes referred
[144]. Defect mobility was found to rely largely on to as the orientational correlation length, is
Fig. 11. AFM images showing examples of topological defects which are commonly observed in single layer thick cylinder-forming BCP
lms. The repeat spacing of the cylinders is 50 nm. (a) A dislocation of PMMA (bright), (b) a disclination pair: (12) PMMA and (12) PS,
(c) a disclination pair: (12) PMMA and (12) PMMA, and (c) a disclination pair: (12) PS and (12) PMMA. (Reproduced with permission
from Hahm et al. J Chem Phys (2001) American Chemical Society [150].)
ARTICLE IN PRESS
annihilation of disclination pairs with opposite sign. for the orientational correlation length, but
This process can occur through different mechan- different power laws (15) for the distance between
isms: (1) annihilation of a single dipolar disclination defects [156].
pair creates multiple same-sign dislocations or (2) Whereas most microscopy studies of BCP lm
multiple disclinations forming a tripole or quadru- dynamics are performed at room temperature
pole annihilate creating fewer, if any, dislocations, following quenching from an ex situ thermal
depending on the specic topology of the original annealing cycle, recent advances in elevated-tem-
pairs. That latter mechanism, which involves an perature imaging with AFM have facilitated in situ
intricate reconguration through relinking or studies of defect evolution in diblock lms. Obser-
joining [150], is preferred because it results in a ving the motion while it happens permits one both
lower defect density [149,151] (Fig. 12). When a to identify transition states that mediate topological
like-charged disclination pair interacts, it will transformations and to capture transient microdo-
tend to propagate rather than annihilate. The main undulations [152,153]. Fig. 13 contains frames
ordering dynamics of these materials, characterized taken from time-lapse AFM movies obtained by
by the growth of the orientational correlation imaging at about 0.02 Hz that highlight the correla-
length and the average distance between defects, tions of these transitory features. Such studies reveal
are found both by Swift-Hohenberg theory [154] rapid structural uctuations with characteristic
and experiment to follow a power law with length scales on the same order as the domain
the growth exponent of 14 [151,155]. Hexagonal spacing as well as slower, longer wavelength
symmetry BCP lms, that is, those with spherical uctuations that were originally seen in bulk
morphology, display the same power law behavior systems with light scattering [157]. Furthermore,
Fig. 12. AFM images taken from a sequence showing annihilation of a disclination quadrupole (12 disclinations, blue; 12 disclinations, red)
during annealing. The schematics (inset) show an idealized quadrupole conguration analogous to each step. (a) After brief annealing, the
spacing between 12 disclinations is about 17 layers, slightly less for the 12 disclinations. (b) After further annealing, the separation distances
are reduced. Subsequent panels are obtained with 1-min intervals of annealing. (c) The quadrupole has annihilated, leaving a cluster of
about four dislocations. (d) Dislocations repel and separate. (Reproduced with permission from Harrison et al. Science (2000) AAAS
[149]).
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Fig. 13. Selected frames taken from a phase-contrast AFM movie of cylinder-forming PS-b-PB showing (a) undulations along the PS
cylinder axes. The dashed lines in frames 211 and 212 are copied from frame 211 and are shown as a guide to the eye to illustrate the
propagation of the undulations. The arrows in frames 210 and 211 indicate correlated undulations. (b) Correlated waviness in the
neighboring domains (indicated by arrows in frame 152) induced by the development of a dotlike defect. (Reproduced with permission
from Tsarkova et al. Langmuir (2006) American Chemical Society [152].)
time-lapse observations, supported by dynamic self- 4. Guiding assembly in the bulk

consistent eld theory, indicate that transition states
can include collective behavior in which local areas Block copolymer melts and solutions are of
temporarily transform into various alternate BCP signicant interest in applications as disparate
morphologies to facilitate defect evolution processes as ltration [159], optoelectronics [160], and sensor
[152]. Ordering kinetics have also been observed to technology [161]. For many end uses, mechanical
change non-monotonically near the orderdisorder properties of these complex uids are of pivotal
transition temperature using elevated temperature importance, and the orientation of the nanoscopic
imaging [158]. domains plays a critical role in determining the
While a complete understanding of defect beha- physical behavior [162165]. The phase behavior
vior has not yet been achieved, it is clear that of BCP in solution is different from that in the
thermal annealing alone will never produce true melt due to solvent and monomermonomer inter-
global long-range order in BCP materials. Pure actions, but similar alignment techniques are
bottom-up self-assembly processes have remarkable applied to both. Flow elds are the most common
advantages over traditional methods for creating tool used to control morphological orientation, and
nanostructures, but they too have inherent limita- Hamley has reviewed the effects of ow on BCP
tions. Only by combining top-down and bottom-up domain order with a particular focus on shear elds
methodologies can one achieve arbitrary control [166,167]. Theorists have paid increasingly greater
over the long-range order in nanoscale materials attention to BCP alignment in recent years, with the
without incurring extraordinary expense. Covering bulk of the effort targeted at understanding the
the full breadth of directed self-assembly is beyond effect of electric elds. Recently, it has been shown
the scope of this review, but the following sections that rather simple theoretical treatments can accu-
summarize many of the efforts that have been taken rately model BCP behavior in the melt, opening up
to apply this approach to block copolymers in opportunities for exploratory studies in this
various morphologies. area [168].
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4.1. Spherical phase isoprene-block-styrene) (PS-b-PI-b-PS) triblocks,

blended with mineral oil to model industrial
Micellar BCPs have a natural tendency to thermoplastic elastomers, have been shown to adopt
assemble into various ordered structures [169]. spherical lattices with uniaxial symmetry around the
Among the earliest use of shear elds to align rolling direction [183]. Recently, the same triblock
BCP domains, Mortensen et al. employed oscilla- has also been aligned using elongational ow
tory shear in both Couette type and parallel plate deformation [184]. This study found that, under
cells to form ordered body-centered-cubic (bcc) certain ow conditions, the native bcc spheres were
lattices of micellar poly(ethylene oxide-block-pro- transformed into cylindrical microstructures with
pylene oxide-block-ethylene oxide) (PEO-b-PPO-b- short-range order. Sphere-to-cylinder transforma-
PEO) triblock copolymers [170172]. This structure tion has also been observed as a result of roll-
is characterized by quasi-long-range order in the casting [185]. The reverse process is an alternative
bond length but true long-range order in the bond route to producing aligned bcc spherical domains by
angle. Order-disorder transitions in this system were rst shear-aligning cylindrical features and then
subsequently studied in greater detail [173], as were heating through the cylinder-to-sphere transition
more in depth structural experiments using small- [186]. Electric elds, typically of 220 V, can also be
angle neutron scattering (SANS) [174]. In general, exploited for BCP alignment for systems in which
shear alignment cannot produce true single crystal there is a sufcient dielectric constant contrast
structures but rather twinned crystals with long- between the polymer blocks. SCF theory has been
range order [175]. A closely related diblock analog used to probe the electric eld inducement of order
of this polymer, poly(ethylene oxide-block-butylene in bcc spherical lattices as well as the transition from
oxide) (PEO-b-PBO), which self-assembles into a spheres to cylinders [187].
face-centered-cubic (fcc) lattice, was found to
respond qualitatively differently under different 4.2. Cylindrical phase
shear rates as studied with SAXS [176]. Steady
shear was found to induce orientation of hexagonal Work on alignment of cylindrical phase BCP bulk
close-packed (hcp) planes both parallel and perpen- materials was originally initiated by motivation to
dicular to the shear plane with a layer sliding understand the structureperformance relationship
mechanism at low shear rates, reorientation of hcp in thermoplastic elastomers [188190]. These re-
planes at intermediate shear rates, and rearrange- searchers extruded a PS-b-PB-b-PS triblock melt
ment into an fcc structure at high shear rates. into a capillary tube thereby producing an axially
Careful control of shear parameters permits one to aligned morphology. A related approach involving
manipulate the crystallographic texture of bcc both solution ow through a tube and controlled
phases in great detail [177,178]. Epitaxial transfor- solvent evaporation to align cylindrical diblock
mation between fcc and bcc structures in diblock copolymer domains was recently reported [191].
copolymers prepared via shear orientation has also Extrusion techniques have also been successfully
been reported [179]. Interestingly, shear can also applied to cylindrical pentablock copolymers [192].
induce disordering in BCP bcc systems above a Oscillatory shear between parallel plates, which
critical shear stress value [180,181]. Density-func- provides greater control over the processing para-
tional simulations have successfully modeled the meters, was rst applied to cylindrical BCP domains
experimentally observed effects of shear on orienta- by Hadziioannou et al. [193,194]. Nearly single-
tional order in BCP spherical systems [182]. In these crystal domains of PS-b-PI-b-PS triblocks aligned
simulations, some results of which are depicted in with the shear direction were obtained using this
Fig. 14, reproduce the experimental result that method. As with spherical domains, elongational
spheres are reversibly elongated at high shear rates. ow can also produce long-range order in cylinder-
Spherical lattices can also be orientationally forming materials. Drawing a press-molded sample,
ordered using roll-casting, in which concentrated Hashimoto et al. [195] successfully obtained macro-
BCP solution is rolled between two counter-rotating scopic alignment of PS-b-PB-b-PS BCP melts.
cylinders while the solvent evaporates. While the Fig. 15 is an electron micrograph showing the
resulting product of this process is a lm, it is long-range order obtained using this method, where
classied as a bulk material in comparison to the the cylindrical domains are imaged end-on. The
thin lms described in Section 5. Poly(styrene-block- same triblock has also been aligned using both
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Fig. 14. Snapshots from dynamic density functional theory simulations of spherical phase BCP under steady shear. The arrow indicates
the shear direction. At the shear rate simulated here, the spheres begin to elongate and the system ows by sliding layers. (Reproduced with
permission from Zvelindovsky et al. Europhys Lett (2003) EDP Sciences [182].)
oscillatory and unidirectional shear elds in a cone- shear ow effects on cylindrical BCPs suggest that
and-plate rheometer [196,197], planar extension parallel and perpendicular orientations are stable at
[198], roll-casting [199201], solvent swelling in low and high shear rates, respectively [206], though
combination with roll-casting [202], and thermal the latter is rarely observed experimentally. Inter-
annealing in combination with roll-casting [203]. estingly, incorporating an anisotropic silicate layer
The latter two methods, due to the combination of into a cylinder-forming triblock copolymer can,
alignment mechanisms, lead to the highest level of under specic oscillatory shear conditions, lead to
orientational order. Indeed, both successive and improved alignment in the polymerclay composite
simultaneous eld applications (electric and shear) compared to the neat polymer [207]. Optical
have been modeled theoretically with a numerical birefringence and depolarized light scattering have
cell dynamic system, and while both sequences also been used to track the effect of shear ow on
produce aligned structures, the concurrent approach diblock copolymer orientation [208], where it was
is the most effective [204]. Cylindrical PEO-b-PBO determined that fast shear ow could align 97% of
has been aligned in a Couette cell with steady shear the material. Analysis of these data is complicated
ow in an experiment in which an optimal shear by the fact that domains aligned far from the shear
rate, resulting in approximately 60% alignment, was direction have extremely poor signal, though
determined by SAXS monitoring [205]. Time- methods have been developed to interpret the
dependent GinzburgLandau simulation studies of experimental observations [209].
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Fig. 15. Electron micrograph of macroscopically oriented cylindrical triblock copolymer domains following press molding. The cylinders
are viewed end-on in this image. (Reproduced with permission from Pakula et al. Macromolecules (1985) American Chemical Society
[195].)
An important class of cylindrical BCPs is those lateral mesogen packing and the meridian contains
containing liquid crystalline (LC) or crystalline the smectic layer reection. The sharp reections in
blocks. The tendency of polymer blocks to crystallize the SAXS pattern (c) highlight the good lateral order
and of the BCP to self-organize into a cylindrical of the cylindrical domains.
morphology makes for an interesting competition
[210212]. Conning the crystalline block to cylind- 4.3. Lamellar phase
rical domains hinders the establishment of defects,
making these systems among the best-aligned Lamellar BCP materials are the most broadly
nanomaterials [213]. The precise molecular orienta- studied morphology for alignment due both to their
tion of the crystalline block can actually depend on industrial utility and their phenomenological sim-
the crystallization temperature. When the crystal- plicity. As with the cylindrical phase, shear ows
lization temperature is very low, the orientation is have been frequently applied to align lamellae. In
generally random within the conning cylinders, early studies of poly(ethylene-alt-propylene-block-
whereas the orientation is perpendicular to the ethylethylene) (PEP-b-PEE), Koppi et al. [220]
cylinders when the crystallization temperature is reported that, near the orderdisorder transition
high [212]. Oscillatory shear methods have been used temperature, dynamic shearing could produce
to align both diblock and triblock LC copolymers domains aligned either parallel or perpendicular to
[214216]. Even more effective than shear ows, the shear direction, depending on the shear fre-
magnetic elds can also align LC BCPs. Advantages quency. The crossover occurs at a frequency that is
of magnetic alignment include that sample shape is approximately the inverse of the characteristic
largely irrelevant, dielectric breakdown is not a relaxation time for local domain deformations.
concern as it is with electric eld alignment, and Parallel alignment is associated with irreversible
magnetic elds pervade space and can be applied inhomogeneous deformation while perpendicular
under various atmospheric conditions [217219]. alignment is the result of more homogeneous
Fig. 16, depicting several X-ray scattering patterns, deformation [221]. Regardless of the frequency
illustrates the effectiveness of this method. The halo regime, alignment proceeds through a two-stage
on the equator in panel (a) originates from the process in which the rst stage is faster than the
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Fig. 16. (a and b) Wide angle X-ray scattering patterns of a magnetically aligned LC BCP. (c) Small angle X-ray scattering pattern of the
same. Enhanced orientation with the magnetic eld is clearly observed for both the mesophase and the cylindrical domains. (Reproduced
with permission from Tomikawa et al. Jpn J Appl Phys (2005) Institute of Pure and Applied Physics [217].)
second [222,223]. Shearing at low temperature or in shear-cell walls [234,235]. Interestingly, when one
a high segregation regime can produce a biaxial observes the domains localized near the shearing
orientation of lamellae, as monitored with in situ surfaces, the parallel orientation is always observed
SAXS [224]. Biaxial structure is a product of the regardless of the morphology in the bulk melt [236].
initial, faster process, whereas the subsequent slow The source of this near-surface region, which
relaxation ultimately leads to uniaxial alignment. extends about 2 mm into the bulk (Fig. 17), is due
There are also reports of stable mixed morpholo- to the contrast in the interfacial energies of the
gies, in which the global structure behaves accord- polymer blocks. While most studies focus on
ing to a linear combination of the viscoelastic diblock copolymers, Bates et al. have demonstrated
properties of the parallel and perpendicular orienta- that multiblock copolymers, as large as undeca-
tions [225]. Molecular weight of the polymer plays block copolymers, can also be aligned using
an important role in determining the mechanistic oscillatory shear [237239]. The multiblock nature
sequence and orientation selection in shear-aligned of this material provides a mechanical coupling
BCPs because entanglement effects, which vary between neighboring lamellar domains, thereby
greatly with the length of the polymer chains, can restricting the available orientations under certain
dominate the dynamics [226]. shear conditions. Whether the polymer chains
Oscillatory shear has also been used to align PS-b- connect domains in loop or bridge conformations
PI diblocks, where strain amplitudes as low as 5%, is a critical factor in whether or not layer-by-layer
surprisingly, were still found to be effective [227]. sliding is permitted. Similar morphological con-
More detailed experiments on the parallel alignment straints have been observed with triblock copoly-
of this polymer revealed that the highest level of mers as well [240]. A third orientation, orthogonal
order was achieved by quenching from the dis- to both the parallel and perpendicular orientations
ordered state to the ordered state, though even with and known as the transverse orientation, has been
this treatment there were still a signicant number observed in these multiblock copolymers [192,237].
of intermediate range wall defects [228]. With this Fig. 18 contains schematic representations of the
polymer, the frequency dependence of the alignment three orthogonal lamellae orientations. The role of
orientation is more complex than that of PEP-b- the transverse orientation, in which it relieves layer
PEE [229]. Biaxial morphologies are also observed compression that results from shear ow, has been
with this polymer [230,231]. The specic response of highlighted with model simulations [241]. Solution
a particular BCP to oscillatory shear is largely extrusion alignment techniques have also been used
determined by the contrast in the viscoelastic to orient multiblock copolymers [192,242]. This
properties of the various blocks. Chen and Korn- process can generate the transverse orientation as
eld have published a review summarizing these well, and, as with shear processing, the number of
early experimental observations of shear alignment blocks in the copolymer rheologically impacts the
[232]. Reorientation from parallel to perpendicular alignment behavior in profound ways.
[233], sometimes referred to as the double-ip Steady shear, discussed from the theoretical
phenomenon, has been described theoretically and standpoint by Fredrickson [243] and others
is a product of interactions between the melt and the [244247], has been employed by Winey et al. to
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Fig. 17. Transmission electron micrograph of perpendicularly aligned BCP, obtained near the surface (right side of image). Adjacent to
the surface, lamellae are aligned parallel, but they become perpendicular away from the surface. The boundary between these regions
occurs approximately 2 mm from the surface and is visible in the micrograph. (Reproduced with permission from Laurer et al.
Macromolecules (1999) American Chemical Society [236].)
Fig. 18. Schematic representations of the principal orthogonal orientations for lamellae under shear. The shear direction is to the right.
minimize complications due to the forwardreverse where there is not [206]. While the majority of
vacillation of oscillatory techniques [248]. This studies address BCP melts, solvated BCP lamellae
effort revealed that lamellar rotation, rather than can also be aligned using shear ow [252255]. An
dissolution/reformation, was responsible for the interesting difference between these systems is that
observed alignment. Kink bands, the topological multilamellar vesicles, so-called onions [256], can
structure via which lamellae typically rotate, have form in the latter. Studies comparing the shear ow
been well described both experimentally and theo- phase diagrams of diblocks comprised of different
retically [249]. Organizing lamellae into aligned polymeric materials conclude that solvated diblocks
structures reduces both the zero shear viscosity containing blocks with similar viscosities display
and compliance compared to the disordered state, comparatively small regions of biaxial morphology
proving that viscoelastic properties depend strongly [257,258].
on microdomain order [250]. As with oscillatory In addition to shear, other mechanical ow elds
shear, steady sheared BCPs display a notable have been used to align lamellar microdomains in
molecular weight dependence regarding their orien- BCP melts and solutions. Compressions deforma-
tation mechanisms [251]. Rather than adjusting the tion of PS-b-PB-b-PS triblock copolymers produce
molecular weight, another parameter of interest is oriented domains with enhanced mechanical prop-
temperature. Simulations have probed the tempera- erties such as rigidity, heat resistance, and deforma-
ture jump-induced phase transitions between lamel- tion resistance [259]; theoretical descriptions of the
lar and cylindrical morphologies under steady behavior of lamellae to compressive stress have also
shear, and have identied mechanistic differences been reported [260]. Pioneered by Cohen et al.,
between systems in which there is shear and those uniaxial compression has been applied extensively
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Though not as prevalent, non-mechanical eld

gradients have also been used to manipulate
lamellar microdomain orientation. A temperature
gradient, in the form of a propagating front, can be
applied in a zone annealing device to draw lamellar
domains into a preferred orientation [271,272].
Fig. 20a shows a schematic of this device. This
device produces a sharp, moving rT along one axis
where rT is in the range of 3070 1C/mm. Using
this method, it is possible to produce extraordinarily
low defect densities (Fig. 20b), but the process is
rather slow compared to alternative approaches.
Fig. 19. Schematic of compressive channel die apparatus used to Electric elds, which take advantage of dielectric
orient triblock copolymer lamellae. The directions identied in constant contrast between polymer blocks, are
the gure are the lateral constraint direction (CD), the ow
direction (FD), and the loading direction (LD). (Reproduced
somewhat more commonly used as an alignment
with permission from Konas et al. Macromolecules (1995) tool. The driving force is proportional to the square
American Chemical Society [264].) of the product of the dielectric contrast and the
electric eld. Alignment by an electric eld offers the
possibility of spatially localizing the eld to dene
to semicrystalline diblock and triblock copolymers selected regions with different orientations. Amund-
[261265]. In these experiments, a channel die son and coworkers [141,142,273] introduced this
connes the polymer and, when heated, permits technique with PS-b-PMMA diblock copolymers
ow only along the channel direction, which thereby sandwiched between two electrodes in a poling
denes a preferred orientation that depends on the apparatus. A representative electron micrograph
processing temperature. A schematic of the channel depicting lamellar alignment along the eld direc-
die apparatus is shown in Fig. 19. Other groups tion is shown in Fig. 21. They report the mechanism
have applied oscillatory shear techniques to align of this effect to be movement of defects rather than
semicrystalline BCPs, where the crystallization disordering/reordering. Theoretical frameworks,
temperature can play an important role in determin- which explain the observations well, have been
ing the ultimate orientation of the crystals with published [274,275]. While most studies invoke dc
respect to the lamellar domains [211,266]. Interest- elds, application of time-varying elds can induce
ingly, while magnetic elds can successfully align a competing alignment mechanism. Tsori et al. [276]
cylindrical domains of ferroelectric liquid crystalline have reported that residual ions in the polymer,
diblock copolymers as detailed in the previous leftover from anionic synthesis, can exert a powerful
section, lamellar samples exhibit no preferred orienting force on lamellae when exposed to low-
orientation following application of a magnetic eld frequency electric elds. BCPs with large molecular
[218]. Roll-casting is another mechanical ow weights and corresponding high viscosities are
technique that has been used to align lamellae, difcult to align with electric elds in melt systems,
including liquid crystalline BCPs [267]. Albalak and effectively limiting the thickness of the samples. For
Thomas [201] rst applied this approach, using a this reason, others have turned to electric eld
PS-b-PEP diblock, and achieved near single-crystal alignment in concentrated solutions [277281]. In
structure. The alignment mechanism was posited to these experiments, a dc eld is applied during
be that the two polymer blocks can be regarded as a solvent evaporation. The presence of the solvent
bilayer of brushes which stretch in the ow diminished the effective dielectric contrast between
direction. Subsequent work combining thermal the blocks, but the mechanical advantage of
annealing and selective solvent swelling with roll- reducing the viscosity makes up for this conse-
casting effectively oriented PS-b-PB-b-PS triblock quence. In solution, the alignment mechanism can
copolymers as well [202,203,268]. Incorporating be either nucleation and growth of domains or grain
clay silicates into this triblock can drastically rotation, depending on the initial morphology of the
improve mechanical properties, drawing on the material [280]. Some recent simulations have sug-
global orientation created as a result of roll-casting gested that, rather than relying on a single orienting
[269,270]. eld, long-range ordered lamellar structures can be
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Fig. 20. (a) Schematic of the temperature gradient cell. (b) Transmission electron micrograph of a single lamellar grain prepared by the
zone heating process. (Reproduced with permission from Bodycomb et al. Macromolecules (1999) American Chemical Society [272].)
ARTICLE IN PRESS
achieved by combining multiple, orthogonal exter-

nal elds [204,282].
4.4. Other phases
The bicontinuous gyroid phase of BCPs has

captured a great deal of attention in recent years
due in large part to potential applications in mass
transport and high-surface area membranes. This
phase resides between the cylinder and lamellar
phases, close to the orderdisorder transition. Many
of the same techniques that are discussed above
have also been employed to orient such bicontin-
uous structures. Shear alignment techniques can be
applied to the gyroid phase [283] and can actually
drive orderorder transitions [284,285]. As with the
cubic spherical phase, cubic gyroid systems aligned
with shear have unavoidable twin grain boundaries.
Roll-casting has also been used to produce aligned
gyroid diblocks and triblocks [286,287]. Tensile
drawing is effective as well [288]. Another phase,
the hexagonal-perforated layer structure (Fig. 22), is
a long-lived non-equilibrium phase that is involved
Fig. 21. Transmission electron micrograph of a microtome slice in the formation of the gyroid phase. Oscillatory
of PS-b-PMMA lamellae aligned using an electric eld. The shear has been used extensively to orient this
direction of the applied eld is indicated. (Reproduced with metastable phase in BCP melts [284,285,289291].
permission from Amundson et al. Macromolecules (1994)
American Chemical Society [142].)
5. Guiding assembly in thin lms
Interest in thin lms of BCPs, though they have

been studied for decades, has surpassed that of bulk
Fig. 22. Schematic of the metastable hexagonal perforated lamellae morphology. The structure is bicontinuous.
ARTICLE IN PRESS
BCPs in recent years [292,293]. This upsurge in affectedespecially in the layers closest to the
attention is due in large part to potential device interfaces [295]. Another consequence of these
applications such as nanowire arrays, patterned interfacial interactions is a quantization of lm
magnetic media, and photonic crystal wave guides. thickness [292], sometimes referred to as terra-
In the thin lm limit, the population of polymer cing. To understand this phenomenon, imagine the
molecules at or near interfaces is a signicantly example of a symmetric-wetting diblock. With such
higher percentage than in melts, so interfaces play a a material, a lm one molecular layer thick will be
more central part in the orientation and order of frustrated because block A cannot wet both the
microdomains [294]. While 2-D ordering is in one substrate and the free interface. The thinnest stable
sense easier than in 3-D because both the quantity lm of this material will be two molecules thick with
of domains to be aligned and the topological the B block constrained inside the lm, surrounded
degrees of freedom are decreased, cylindrical and on top and bottom by A blocks. This thickness is
lamellar morphologies can encounter new kinetic denoted L, and an extension of this argument
traps as a result of the connement, thereby leads one to the conclusion that only lms with
complicating the alignment process. Introducing a thickness nL, where n is an integer, are allowed. An
surface to a block copolymer establishes a new analogous analysis of asymmetric-wetting diblocks
constraint on the system. Generally, one of the leads to a quantization restriction of (2n+1)(L/2).
polymer blocks will preferentially wet the substrate Fig. 23 displays schematics of these two wetting
and one of the blocks, perhaps the same one, will scenarios for the lamellar phase, though an analo-
preferentially wet the free interface. Minimization of gous situation applies to the other morphologies as
the surface energies drives this selective wetting. If well.
the surface energies of the blocks are similar, the
volume fraction of the blocks can also affect the 5.1. Spherical phase
interfacial presentations. For example, if the min-
ority component has a surface energy just a little Among the earliest observations of the prefer-
smaller than the majority component, it may be ential surface wetting effect in the spherical phase
energetically more favorable for the minority block were those that involved monitoring the structure of
to form microdomains of the morphology appro- PS-b-PB thin lms with transmission electron
priate for the specic volume fraction rather than microscopy (TEM) [296]. These were followed by
wetting the interface. In lms thick enough to secondary ion mass spectrometry (SIMS) experi-
accommodate multiple domain layers, one expects ments on PS-b-PVP lms by Kramer et al. [297].
the microdomains to form lattice structures as in the Angelescu et al. [298] have recently applied shear
bulk; however, the interlayer spacing can be orientation techniques to align spherical phase
Fig. 23. Schematics showing the effect of selective interfacial wetting in BCP thin lms. When both interfaces are wet by the same block
(symmetric wetting), lm thicknesses are quantized to integer multiples of L. In the case of asymmetric wetting, the quantization rule
changes to (2n+1)(L/2). In either case, the selective wetting leads to a parallel orientation of the BCP domains with respect to the substrate
plane.
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PS-b-PEP. In this experiment, the effect of shear on thin lm nature of the system. Thin lm spherical
lms of various thicknesses in the proximity of the phase systems display rst-order melting transitions
ideal two-layer thickness was investigated, and it with temperature similar to the bulk ODT [306]. It
was observed that only lms of precise (72%) has also been shown that, if one prepares a lm of
bilayer thickness were well-ordered following shear spherical BCPs that is not of a stable quantized
processing. Orientation was represented by one of thickness on a patterned substrate, the channels will
the hexagonal lattice vectors aligning with the shear attract the excess material and thereby produce a
direction. Molecular dynamics simulations of the more uniform lm [307]. Cheng et al. [308311] have
same system were performed to determine the extended graphoepitaxy experiments to PS-b-PFS
ordering kinetics [299]. These simulations revealed spherical diblock copolymer systems, motivated by
that, while ordering kinetics in the absence of shear the usefulness of this material in nanolithographic
follow slow power-law scaling, shear-induced order- applications as described in Section 2. The max-
ing proceeds by an initial fast exponential process imum channel width for which single-grains were
followed by linear growth. SCF theory has been achieved in these experiments, 270 nm, was signi-
employed to investigate the effect of interface cantly shorter than that reported by Segalman et al.,
potentials and lm thicknesses for spherical phase though it was still roughly ten times the polymer
triblock copolymers, which are notably more com- domain spacing of 29 nm. This discrepancy is likely
plex due to the increased parameter space [300]. attributable to kinetic effects stemming from the
The most popular technique for achieving long- higher glass transition temperature. Substrate topo-
range order in lms with spherical morphology is graphy for graphoepitaxy is not restricted to square-
graphoepitaxy [301]. In this approach, originally wave patterns. Triangular channels have also been
developed for inorganic materials and liquid crys- demonstrated as directing agents for spherical BCP
tals [302], substrate topography guides the epitaxial domains [312]. In these grooves, the domains adopt
growth of a crystalline lm. A traditional approach a fcc symmetry with the top surface displaying a
is to create surface relief features that match the square symmetry as opposed to the more common
domain periodicity and shape of the BCP, though hexagonal symmetry (Fig. 25). To take up the issue
this largely defeats one of the principal advantages of addressability in these systems, prompted largely
of BCPs for applicationsnamely, that they self- by patterned media applications, Cheng et al. [309]
assemble into structures on the nanoscale without introduced small, sharp edge features on the
top-down intervention. Graphoepitaxy, on the channel sidewalls to pin the array. Indeed, illustrat-
other hand, can utilize topography on length scales ing the potential of these materials, a group at
many times the BCP domain length scale. Segalman Toshiba Corporation has developed prototype
et al. [303] were the rst to apply this technique to platters for circumferential patterned media based
spherical phase block copolymers. In this study, the upon the graphoepitaxy-directed self-assembly of
substrate was pre-patterned with 4.5 mm square- PS-b-PMMA spherical phase BCPs (Fig. 26)
wave channels that effectively directed the long- [25,32,33]. In a twist on this methodology, Nealy
range ordering of 27 nm PS-b-PVP spheres. The et al. have used topographically patterned sub-
polymer lms were precast and then oated onto the strates to align cylindrical domains and then driven
channeled substrate. Ordering is nucleated by the a cylinder-to-sphere transition via thermochemical
channel sidewalls, and they found that the max- methods to produce well-ordered arrays of spheres
imum width for the channels that would support in channels [313]. A related approach is to prepare
single-grain structures was 5 mm. Fig. 24 depicts an elastomeric molds that can deposit submicron
AFM image of a nearly perfect domain of ordered patterns of spherical BCPs onto substrates using
spheres on a topographically patterned substrate, microcontact printing, although the long-range
supported by Voronoi and Fourier transform order in these products is much weaker than in
analyses. Orderdisorder transitions in these sys- those produced by graphoepitaxy [314].
tems have been investigated, and it has been
established that the (continuous) transition from 5.2. Cylindrical phase
hexagonal packing to disordered liquid occurs at a
higher temperature (lower wN) than in the bulk Lithographic applications in which 1-D structures
[304,305]. This orientational stabilization is attribu- are desirable are best accomplished using cylindrical
table to the lateral connement rather than to the morphologies. For such ends, alignment parallel to
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Fig. 24. A 1.5 1.5 mm region of a spherical BCP lm on a mesa of a topographically patterned substrate. (a) Atomic force micrograph of
the region after etching with SIMS indicating that the single grain is near perfect. (b) Voronoi diagram constructed from the sphere center
locations. Six-fold-coordinated sites are unshaded while 5-fold sites are magenta and 7-fold sites are blue. The presence of one 57 pair
indicates the presence of a single dislocation in the image. (c) Fourier transform of the image. The sharp rst-order peaks equidistant from
the center support the view that this is a single crystalline, hexagonal grain. The presence of higher-order peaks attests to the high degree of
order. (Reproduced with permission from Segalman et al. Macromolecules (2003) American Chemical Society [304]).
the substrate is typically critical. There are also 5.2.1. Oriented parallel to the substrate
many applications, ranging from membranes to Thin lms of cylinder-forming BCPs are impacted
patterned storage media, in which pores are a by interface interactions in the same manner as spheres,
valuable architecture. These functions require align- though the consequence of preferential wetting in this
ment perpendicular to the substrate. Both orienta- case forces the cylinders to lie parallel to the lm plane
tions are discussed in the following sections. [296,316319]; this is also the case for freestanding
Compared to the spherical phase, behavior of lms [320]. Solvent evaporation rate can impact the
cylindrical systems is somewhat more complicated. cylinder orientation with respect to the substrate,
This increased complexity is a source of funda- though this is a kinetic effect and does not represent
mental interest, practical frustration, and in some the equilibrium structure [321], whereas orientation
cases novel behavior. An example of such complex dependence on lm thickness is governed by thermo-
behavior is highlighted by the intricate response to dynamic factors [322]. If the interaction of the polymer
swelling with selective solvents that has been with the substrate is too strong, the orientational
reported for diblock and triblock cylindrical lms persistence length will be limited. This effect can be
[315]. In some cases, such swelling can have useful countered by introducing a polymer brush buffer layer
effects on the orientation of the microdomains. to mitigate the substrate interaction [323].
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Fig. 25. Scanning electron micrographs of etched PS-b-PFS lms in triangular grooves. (a) Square packing of spheres is visible in the top
view; (b) the same sample as that in part (a) in a cross-sectional view showing a sphere array with 11 rows; (c) the polymer directly adjacent
to the groove surfaces shows a hexagonal arrangement. (Reproduced with permission from Chuang et al. Nano Letters (2006) American
Chemical Society [312].)
ARTICLE IN PRESS
Fig. 26. Scanning electron micrograph (a) of nanopatterned CoPtCr magnetic dots prepared by graphoepitaxy and block copolymer
lithography on a 2.5-in hard disk drive glass plate (b). (Reproduced with permission from Naito et al. IEEE Trans Mag (2002) IEEE [33].)
Not surprisingly, ow elds have been proven graphoepitaxy to cylindrical thin lms [328]. Initi-
effective at aligning thin lms of cylinders just as ally, this approach led to the non-intuitive result of
they have with other morphologies in the bulk and cylinders oriented perpendicular to the channel
in lms. One such approach is droplet pinning [324]. propagation direction (Fig. 28). The channel depth
This method entails pinning the upper edge of a in this study was approximately an order of
droplet of BCP solution on a tilted substrate. As the magnitude larger than the polymer layer spacing,
solvent evaporates, there is a net ow of solution and several layers were deposited into the channels.
toward the pinned edge that couples with an Perpendicular alignment originated from polymer
ordering front that nucleates at the free surface. owing away from the center of the channels
Together, these elds act to align the cylindrical toward the sidewalls driven by capillary action.
microdomains over lateral distances as long as Cylindrical microdomains are pulled in the direction
20 mm. An approach that rivals droplet pinning for of this ow. Annealing for longer times continues to
correlation length and surpasses it in speed, aligning remove material from the center of the channels,
large regions in a matter of seconds, is directional eventually producing a featureless L/2 region. The
crystallization [325]. A molten, crystalline organic oriented cylinders are, therefore, a metastable
material, such as benzoic acid or anthracene, is used structure. Film thicknesses generated using these
as the solvent for the BCP. When the system is various methods correspond primarily to multiple
cooled below the crystallization temperature, a layers, whereas single layers are of the greatest value
directional solidication process is initiated that for lithographic applications.
orients the polymer microdomains parallel to the One route to align monolayer cylindrical lms is
fast growth direction (Fig. 27). Coupling directional by shear ow, though applying a shear to an
crystallization with a semicrystalline BCP can create ultrathin lm is non-trivial. Angelescu et al. [329]
epitaxial growth of the crystalline block leading to a attained this goal by applying a weighted, unpat-
variety of interesting microstructures [326]. An- terned elastomeric stamp to the top of the BCP lm
other, less controllable method involves wetting and generating a controlled, uniaxial lateral force
the substrate with a polar solvent prior to casting on the weight. This technique resulted in nearly
the BCP lm [327]. Because the diblock does not wet defect-free lms over the entire area over which the
the polar solvent well, it tends to dewet from the pad traveled. Sibener et al. have further developed
substrate and form annuli of 25 mm diameter. the graphoepitaxial approach to obtain thermody-
Around the perimeter of each annulus, the cylind- namically stable, oriented monolayer cylinders in
rical domains are preferentially radially aligned. The channels [330,331]. In this approach, the channel
authors attributed the observed alignment to sidewalls act as a new set of interfaces for which the
anisotropic drying during annulus formation. Since diblock copolymer will exhibit preferential wetting.
there is no obvious way to dene the location of the Following the logic outlined at the beginning of this
annuli a priori, device applications for this techni- section, this results in alignment of cylinders parallel
que are limited. Greater control over the location of to the substrate sidewalls. Disclination and
oriented domains can be achieved by applying dislocation defects in the center of the channels
ARTICLE IN PRESS
Fig. 27. (a) TEM image of a thin lm of PS-b-PI directionally solidied with benzoic acid. The cylindrical PI microdomains are well
aligned along the fast growth direction of the benzoic acid crystals. No grain boundaries are evident, and only a few dislocation defects are
seen. Inset shows the fast Fourier transform (FFT). Spot-like reections located on the equator indicate a nearly single-crystal
microstructure. (b) Schematic model of the aligned microstructure. Cylindrical PI microdomains are edge-on to the crystalline substrate
and aligned along the b axis of the benzoic acid crystal. (Reproduced with permission from Park et al. Macromolecules (2001) American
Chemical Society [325].)
can be annealed out, resulting in long-range the potential application of such material for
alignment with low defect densities. In contrast to nanotechnology. Elastomeric molds have also been
the limitations observed for channel widths lled demonstrated as effective aids in the long-range
with spherical domains, these experiments demon- orientation of monolayer cylindrical domains
strated that microdomains could be aligned not only [335,336]. Lithographic patterning of substrate
many microns from the edges of the channels, but topography can be coupled with directional crystal-
also both above and laterally beyond the conned lization to fabricate more complex systems with
volume of the channels. In this manner, global control over domains oriented in more than one
alignment of cylindrical domains can be realized direction [337]. Complete elimination of disclination
with the topmost surface being at despite the and dislocation defects can be realized by lithogra-
underlying channel corrugation that nucleates the phically patterning the substrate with a periodic
orientation (Fig. 29). Black has built on this work, chemical contrast commensurate with the length
using channel-aligned cylindrical domains to fabri- scale of the polymer microdomains [313,338]. This
cate nanowire eld effect transistors out of silicon technique produces perfect nanostructures over
[332,333]. Kramer and coworkers [334] have noted large areas when coupled with interference litho-
that a nite density of thermally generated defects is graphy, and therefore has potential application in
unavoidable in this class of systems, again limiting arenas where the complete absence of defects is
ARTICLE IN PRESS
Fig. 28. Contact mode topographic AFM images of a cylinder-forming PS-b-PMMA thin lm sample spin-cast on a silicon nitride
grating. Before (a) and after (b) the sample is annealed. (c) Phase tapping mode AFM image of lying-down cylindrical domains in the L
thick region when a thin lm of PS-b-PMMA is prepared on a at silicon nitride substrate; no alignment is present with the at substrate.
(d) Phase tapping mode AFM image of the inset in (b). Note the formation of lying-down cylindrical domains which are aligned
perpendicular to the grating lines. (Reproduced with permission from Sundrani et al. Macromolecules (2002) American Chemical Society
[328].)
critical. However, the available structures and, perpendicular to the eld (but parallel to the
ultimately, the fabrication costs are dened by the substrate plane) [341]. This structure also represents
lithographic process itself. a free energy minimum, though, in the absence of
As in the bulk, electric elds can be used to align the surface, parallel alignment is always more
BCP domains in thin lms. Morkved et al. [339] stable. A theoretical treatment of this balance of
introduced this approach with an experiment in energies was recently reported by Lin and Schick
which planar electrodes were patterned onto a [342].
surface prior to casting of a PS-b-PMMA cylind- Recently, several groups have begun to apply
rical thin lm. Applying an electric eld on the optical techniques not to probe cylinder alignment
order of 30 kV/cm and annealing above the polymer but, rather, to induce it in liquid crystalline
Tg, they were able to orient the cylindrical domains BCPs. Diblocks composed of exible PEO and
parallel to the eld lines (Fig. 30). In the initial poly(methacrylate) (PMA) containing an optically
experiment, alignment was obtained over an area of active azobenzene (AZ) moiety have been aligned
5 mm2, limited by the requirement for a very strong perpendicular to the polarization direction of actinic
eld between the two electrodes. By later patterning light due to supramolecular cooperative motions
interdigitated electrodes, this method was scaled up [343]. In the absence of irradiation, the PEO
to align domains over an area of 2 cm2 [340]. Pairing cylinders will orient themselves perpendicular to
electric elds with preferential surface interactions, the substrate due to stability obtained from smectic
one can also obtain cylindrical domains oriented ordering. Exposure to an Ar+ laser induces
ARTICLE IN PRESS
Fig. 29. Demonstration of the ability of alignment of BCP domains within topographically patterned channels to induce global alignment
of cylindrical domains across the entire surface. Sequential tapping mode phase AFM images of a spin-cast thin lm PS-b-PEP sample
following annealing. The troughs have an 11L/2-thick lm whereas crests have a 3L/2-thick lm. (Reproduced with permission from
Sundrani et al. Langmuir (2004) American Chemical Society [330].)
alignment parallel to the substrate over the full 5.2.2. Oriented perpendicular to the substrate
exposed area. Those regions not exposed to the AFM is frequently used to identify the orienta-
laser remain in their native perpendicular state. tion of cylinders in thin lms, where contrast
It has been demonstrated that the structure of between 0-D (perpendicular) and 1-D (parallel)
cylindrical BCP thin lms is sensitive to the lm morphologies is readily apparent. However, volume
thickness [318,344346]; this also applies to imaging of cylindrical thin lms realized by stepwise
PEO-b-PMA/AZ liquid crystals. By performing plasma erosion has shown that 0-D features on the
holographic irradiation from argon ion laser light, surface can merge into parallel cylinders below the
Seki et al. [347] have shown that cylinder orientation surface [349]. This fact should be kept in mind
can be laterally modulated across a lm due to whenever interpreting surface-sensitive imaging of
mass transfer into corrugated structures matching cylindrical BCP lms. Preferential wetting of the
the holography pattern. The thickness variation interfaces usually leads cylinders to align parallel to
was sufcient to cross the parallel-to-perpendicular the substrate plane. One can manipulate the surface
transition. Furthermore, by manipulating the energies, however, by a variety of means. One
polarization mode, they were able to select the approach is to deposit the polymer solution on the
in-plane orientation of lying-down cylinders. surface of a bath of deionized water [21]. The
Related simulations have also recently been re- polymer solvent (toluene) does not wet the water
ported by Balazs and coworkers [348], in which they surface, and the resultant chaotic deposition leads
propose a route to defect-free copolymer lms using to metastable domains of perpendicularly oriented
a sweeping, collimated light. Representative images cylinders. In order to improve reproducibility,
from these simulations are presented in Fig. 31. methods relying more on equilibrium phenomena
ARTICLE IN PRESS
Fig. 30. Transmission electron micrographs of cylindrical-phase PS-b-PMMA lms oriented parallel to the substrate plane using electric
elds. The scale bar is 500 nm. (a) Region halfway between the electrodes indicating a transition from good alignment near the central
electrode gap to disorder outside of this gap. (b and c) Regions near a corner of an electrode with the eld applied (b) and not applied (c)
showing that the cylinders follow the eld lines. (Reproduced with permission from Morkved et al. Science (1996) AAAS [339].)
are desirable. Theoretical analysis shows that if the tion, therefore, nucleates the orientation at the top
difference between the surface energies of the surface and extends down into the lm. This
polymer blocks is small and the lm thickness is methodology was rst proposed by Ho et al. [42]
no more than a few lattice spacings, it is possible to using cylinder-forming poly(styrene-block-L-lactide)
create perpendicularly aligned cylinders [318,319]. (PS-b-PLLA). An additional advantage of this
Combining surface energy tuning and nanoimprint particular BCP is that the PLLA cylindrical blocks
lithography, Li and Huck [335] have reported well- can be easily hydrolyzed to produce nanoporous
ordered arrays of perpendicularly oriented cylinders membranes.
of PS-b-PMMA. Alternatively, one can rely on Probably the most common technique used to
directional evaporation to overcome surface energy align cylinders perpendicular to a substrate is
constraints, as with PS-b-PEO diblock copolymers application of an electric eld. In order to overcome
in which the PEO cylindrical domains align normal surface energy effects, a critical strength of an
to the substrate as the solvent is removed from the electric eld must be applied by electrodes of
free surface [350]. Another approach is to employ appropriate dimension [351], which will be a
BCPs that exhibit a strong contrast in solvent function of both the BCP and substrate material
evaporation between the polymer blocks. If a systems. For PS-b-PMMA constrained between Al
solvent is far more likely to evaporate from one electrodes, this critical eld has been reported as
particular block, a direct pathway for evaporation 11.5 V/mm [352], irrespective of lm thickness up to
can be established by aligning those domains 30 mm. The mechanistic details of the reorientation
perpendicular to the free interface. Solvent evapora- from parallel to perpendicular has been investigated
ARTICLE IN PRESS
Fig. 31. Simulations of BCP domain alignment using optical combing. A high intensity, spatially localized beam is rastered over the
sample. This process effectively combs out any defects in the material and creates highly regular structures. (Reproduced with permission
from Travasso et al. Langmuir (2006) American Chemical Society [348].)
by SAXS, SANS, and TEM [353,354]. These studies As with the PS-b-PLLA system, PMMA cylinders
show that the original parallel cylinders uctuate and oriented perpendicular to the substrate can be
then break apart into spherical domains. Spheres selectively removedin this case by UV light or
gradually elongate and reconnect into cylinders with electron beam irradiationand there is an added
the perpendicular orientation. Fig. 32 depicts a series benet in that the PS matrix becomes crosslinked
of electron micrographs during successive annealing during exposure, effectively strengthening the na-
under an electric eld resulting in a perpendicular noporous structure. For applications, it is essential
orientation following 16 h at 185 1C. Interestingly, that the pores traverse the full thickness of the lm,
one can actually drive a spherical phase BCP into a that is, that the electric eld both orient the
cylindrical morphology by applying an electric eld cylinders and remove all discontinuity defects.
[355]. Theoretical treatments of the alignment Cross-sectional TEM analysis of lms prepared in
process are also available [342,356]. These studies this manner do indeed exhibit continuous pores
suggest that the mechanism for reorientation from top to bottom of the lm. Rather than using
depends upon the strength of the surface energy. the pores for transport, ltration, or a nanoelec-
When the surface interactions are weak, the trode array [45], one can also ll them with material
cylinders can reorient without breaking up while to create nanowire arrays [47,48]. Similar morphol-
strong interactions induce more complex processes. ogies, although with somewhat larger periodicities,
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Fig. 32. (a) Schematic diagram of TEM sample preparation. Successive cross-sectional TEM images of PS-b-PMMA lms after annealing
under an electric eld. Scale bar is 100 nm. (e) A snapshot of PS-b-PMMA morphology (3-D TEM tomography of (c)). The box size
corresponds to 1029 nm 740 nm 236 nm. (Reproduced with permission from Xu et al. Macromolecules (2005) American Chemical
Society [354].)
can also be created with binary PS/PMMA materi- ference microscopy, AFM, and X-ray reectivity
als in which the two polymers are not covalently [362,364366].
bound [357]. Parallel orientation is the more straightforward
arrangement, but for many applications, perpendi-
cular orientations are more useful. Theoretical
5.2.3. Lamellar phase analyses have suggested that, while parallel orienta-
Early studies of lamellar orientation in thin lms tions are favored by preferential wetting and by the
revealed that preferential wetting of the interfaces enhanced chain end density near the substrate,
leads the lamellae to align parallel to the substrate, perpendicular orientation is stabilized by the fact
assuming sufcient annealing has been applied to that chains are more easily stretched along the
drive the system into its equilibrium structure [296]. substrate than in the bulk [367,368]. Film
Such alignment is typically referred to as surface- thickness is one key parameter that determines the
induced orientation. Neutron reectivity, SAXS, ultimate orientation [369373]. Perpendicular or-
and SIMS have been used to monitor this process in ientations can also be formed by inserting a short
PS-b-PMMA lamellar BCPs [358362]. Various PB block between the PS and PMMA blocks,
materials exhibit different preferences for the con- thereby creating a triblock copolymer [374,375]. The
stituent polymer blocks. For example, PS selectively PB block has the lowest surface energy and,
wets a gold surface while PMMA wets silicon. PS therefore, prefers to have contact with the free
also exhibits an afnity for the free interface. interface. Covalent connection of this block to the
Because of the penetrating nature of neutrons and end blocks draws them to the free surface as well,
X-rays, these studies also succeeded at measuring thereby forming the perpendicular orientation. As
the width of the interface between the microdo- surface energies drive the typical parallel orienta-
mains within the lamellar lm. Regardless of the tion, it is logical to manipulate parameters that
overall molecular weight of the polymer, this inuence the surface energies in order to gain
interface was found to be about 5 nm wide, though control over the direction of the microdomain
the exact value can be adjusted by tuning the lm orientation. One such approach is to constrain a
thickness [363]. Time evolution of the structures at BCP lm between two solid surfaces [376]. Lam-
the top surface has been characterized with inter- booy et al. [377] were the rst to attempt this
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experimentally. In this study, the lamellae were chemically modifying the substrate. A convenient
always aligned parallel to the conning surfaces, method to accomplish this end is the use of a
regardless of lm thickness. There is, of course, random copolymer brush layer in which the
inherent frustration in the polymer when the lm composition of the copolymer can be tuned to
thickness is not commensurate with the unconned control the interactions with each of the blocks in
lamellar spacing. A straightforward ramication of the lamellar BCP [387]. The random copolymer is
this frustration is a variation in the lamellar spacing chemically grafted onto, for example, a silicon
[378]. Monte Carlo simulations suggested that substrate to modify the interface for subsequent
interplay between the equilibrium lamellar periodi- BCP deposition. When the surface energy is
city and the actual lm thickness could lead to designed to be neutral [388,389], perpendicular
domains tilted away from the parallel plane [379]; domains can be achieved. However, this effect is
subsequent theoretical modeling provided more limited to a region near the modied interface, and
specic constraints on the parameters that could parallel orientation will dominate near the free
lead to perpendicular arrangements [380384]. interface in a sufciently thick lm [390]. Fig. 34
Experimentalists then began to explore the surface depicts SANS data exhibiting characteristics of such
energy and lm thickness parameter space in greater a mixed orientation. In order to achieve improved
detail to home in on the appropriate conditions, orientation control, the surface energy at the free
successfully forming lms with perpendicular or- interface, too, must be tuned. Random copolymer
ientation (Fig. 33) [385,386]. Extension of conne- brushes can also be placed between a BCP lm and
ment to three dimensions is discussed in the next the air interface by linking one end of the chains to
section. peruorinated moieties that have surface energies
Rather than relying on physical connement, one much lower than those of the polymer thereby
can alternatively manipulate surface energies by segregating them to the free surface. By controlling
Fig. 33. TEM images looking down the axis normal to the surfaces of two PS-b-PVP samples in connement and their 2D-Fourier
transforms. The lateral correlations in the image with L/D* 1.05 (where L is the lm thickness and D* is the unconned domain period)
indicates ordering perpendicular to the surfaces while the absence of any structure in the image with L/D* 1.45 suggests lamellar
ordering parallel to the conning surfaces. (Reproduced with permission from Koneripalli et al. Langmuir (1996) American Chemical
Society [386].)
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Fig. 34. SANS data for a sample on a neutral surface, for incidence angles of (a) 901, (b) 601, and (c) 01. The scattering patterns can be
understood with the help of the schematic model shown in (d). The equatorial scattering comes from lamellae oriented parallel to the free
interface while the meridional scattering arises from lamellae oriented perpendicular to the substrate. (Reproduced with permission from
Mansky et al. Macromolecules (1997) American Chemical Society [390].)
both interfaces, it is possible to gain better control patterned with parallel lines that will act as a
over the orientation throughout the lm [391393]. template to assemble BCP microdomains both
Self-assembled monolayers (SAMs) can also be used perpendicular to the substrate and parallel to one
to tailor surface energies and hence to generate another over the full patterned region. One applica-
neutral surfaces. The advantage of using SAMs is tion of this methodology is based on the chemistry
that they can be readily patterned by a variety of of alkylchlorosiloxanes [400402]. The advantages
means. Among the initial experiments in this area of this system include that the wetting behavior can
entailed patterning a SAM to contain regions with be tuned by X-ray exposure, which itself can be
alkyl termination and regions with alcohol termina- performed in a patterned manner to perform
tion [394,395]. It was observed that the hydrocarbon spatially selective surface energy modication
chemistry led to typical parallel orientation while [403,404], and that the SAMs are stable in vacuum
the latter chemistry could produce perpendicular at temperatures as high as 740 K. Using extreme
alignment. Simply patterning regions to contain an ultraviolet lithography in concert with photoresist
alkanethiol SAM and other regions to be free of cast on a polymer brush layer, Nealey and cow-
organics has also been reported [396,397]. Pattern- orkers [405408] have demonstrated defect-free
ing on a length scale comparable to the equilibrium alignment of perpendicularly oriented PS-b-PMMA
lamellar periodicity provides an opportunity to lamellae. This work further showed that blending a
probe an interesting competition between various BCP with excess homopolymer or with a second
driving forces [398,399]. The commensurability BCP of different molecular weight expands the
between the bulk lamellar spacing and the pattern range of accessible structures by facilitating angled
width has signicant inuence on the resulting patterns and continuous period tunability, respec-
orientation. Spatially patterned heterogeneous sur- tively (Fig. 35). A potential challenge associated
faces offer a further advantage in that alignment can with introducing homopolymer is that the lamellar
be controlled in multiple dimensions. For example, periodicity is increased, which will require careful
a surface designed with two chemistries, each tuning of the molecular weights of both the BCP
attracting a different polymer block, can be and the homopolymer in stringent technological
ARTICLE IN PRESS
applications. The effect of chemically patterned non-polar Au domains (Fig. 36). PMMA preferen-
surfaces on the morphology of conned BCP tially wets the silicon oxide while PS wets the gold,
lamellar thin lms has been studied using mean- so when the topographic period is commensurate
eld theory [409,410]. with the lamellar spacing, perpendicular orientation
Topographical patterning, rather than chemical of PS-b-PMMA can be templated with this sub-
patterning, can also be used to direct the self- strate. Liddle et al. [415] have shown that, by
assembly of lamellar domains. The simple introduc- combining graphoepitaxy with chemical patterning,
tion of a corrugated substrate is sufcient to one can produce non-linear arrangements of defect-
introduce orientational anisotropy into thin lms free BCP lamellae without introducing homopoly-
of symmetric BCPs [411]. Film thickness variations mer into the system.
between the peaks and channels resulted in periodic As with other BCP morphologies, various ex-
variation between parallel and perpendicular orien- ternal elds can produce oriented thin lms of
tations. Others have observed unexpected behavior lamellae. Pickett applied SCF calculations to estab-
on topographically patterned surfaces. For instance, lish that thermal gradients could be used to achieve
depending on the depth of the pattern, an overlayer aligned lamellae oriented either parallel or perpen-
of lamellar BCP can either conform to the dicular to the substrate, depending on the direction
topography or display anti-conformal structure of the gradient [416]. This technique has not yet
[412]. This unusual behavior is attributed to a been tested experimentally for lamellar BCP thin
balance of energies associated with interfacial lms. Electric elds, however, have received both
interactions and polymer deformation. Topographic theoretical and experimental attention. Tsori and
patterning can also be combined with chemical Andelman [417], followed by others [418], used
patterning. Adjusting the corrugation periodicity to theoretical techniques to outline the parameters that
be comparable to the lamellar period and evaporat- determine the critical eld necessary to overcome
ing metal onto one edge of the substrate pattern surface energy effects and induce perpendicular
using shadowing effects, Rockford et al. [413,414] orientation throughout the lm. This competition
prepared striped substrates with polar SiOx and between interfacial effects and polarization was then
Fig. 35. SEM images of lamellae oriented perpendicular to the surface in a ternary PS-b-PMMA/PS/PMMA blend. The chemical surface
patterns are fabricated with periodicities of 65, 70, 75, and 80 nm, and the lamellar domains of the block copolymer blend are self-
assembled and registered around 451, 901, and 1351 bends. Perfect long-range order was achieved in the linear portions for all substrate
pattern periodicities, whereas defects arose at the corners of sharp bends in some cases. (Reproduced with permission from Stoykovich
et al. Science (2005) AAAS [406].)
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Fig. 36. SEM image of a periodic heterogeneous surface used to manipulate lamellar BCP orientation. Scale bar is 600 nm. The inset is a
schematic of the glancing angle evaporation geometry used to deposit metal only on one edge of the facets using a shadowing effect.
(Reproduced with permission from Rockford et al. Phys Rev Lett (1999) American Physical Society [413].)
explored in the classic PS-b-PMMA system with microdomain orientation and alignment. Krausch
SAXS, SANS, and TEM [419421]. These experi- et al. [425] exposed a lamellae-forming triblock
ments deciphered the mechanism of reorientation. copolymer to various solvent vapors and investi-
Rather than a simple rotation of domains, lamellae gated the effect of the rate of subsequent evapora-
are rst disordered and then reformed with the eld- tion. Drying induces a mechanical strain eld that
aligned orientation, though the region near the will lead to parallel orientation for slow drying rates
substrate typically remains stubbornly parallel. The and perpendicular orientation for fast drying rates.
effectiveness of electric eld alignment can be A drawback of this approach is that the strain elds
augmented through a variety of means. One are strongest at the surface of the lm, suggesting
approach, outlined in previous sections for other that good alignment may not be present throughout
morphologies, is to apply a sequence of orthogonal the material. Better alignment can be obtained if a
elds. Elongational ow can be teamed with an crystallizable solvent is used [325]. In this method,
electric eld to produce good long-range order in the lm is initially maintained at a temperature
lamellar lms [422]. Complexing ions into one block above the crystallization threshold of the solvent.
of the BCP, by incorporation of halide salts, As the lm is then cooled, a very fast directional
strengthens the contrast in the dielectric constant crystallization initiates which produces perpendicu-
of the blocks and thereby reduces the eld required larly oriented lamellae aligned over large areas.
for alignment [423,424]. In this manner, complete Lamellar BCPs that contain semicrystalline or
reorientation perpendicular to the surface can be liquid crystalline blocks often exhibit surface inter-
achieved. actions that can naturally result in functional
Though typically used simply as a medium for morphologies. Crystallization of semicrystalline
casting lms, solvents can also play a critical role in BCPs can be coupled with controlled dewetting to
ARTICLE IN PRESS
induce long-range lamellar order [426,427]. The congurational frustration induced by the incom-
dewetting process provides a three-phase contact mensurability between the smectic spacing and
line that both nucleates and denes the growth smectic block size, as dened by the BCP period.
direction for crystallization. At appropriate crystal Competition between these two internal length
growth rates, perpendicular lamellae can be ob- scales directs the ultimate orientation of the
tained. Semicrystalline triblock copolymers, in lamellae. Long-range order, however, has not been
which the end groups are PE and the linking block achieved with this method. More complex, hier-
is amorphous, have been oriented using epitaxial archically ordered BCP lms can be created using
crystallization [428,429]. These experiments entailed directional solvent evaporation from rod-coil liquid
matching the unit cells of the PE blocks and the crystalline BCPs (Fig. 37) [431]. These materials
substrate, composed of crystalline benzoic acid or display order at various length scales, which may
anthracene. Lamellar liquid crystalline BCPs com- prove useful in technological arenas.
posed of isotropic and smectic blocks have been
observed to orient either parallel or perpendicular 6. Guiding assembly by three-dimensional
to the surface, depending on whether the BCP was connement
asymmetric or symmetric, respectively [430]. The
source of this effect is two-fold. First, the wetting Conning BCPs within 3-D boundaries, a re-
behavior of the BCP is affected by the relative cently developed concept, was rst studied compu-
proportions of the two blocks. Second, there is a tationally. The previous sections have demonstrated
Fig. 37. AFM images of hierarchical structure in a rod-coil BCP lm obtained following directional solvent evaporation. (a) Low
magnication and (b) and (c) higher magnication images showing the different orientations at various length scales in this system. (d)
Chemical structure of the BCP and a model for the molecular packing. (Reproduced with permission from Park et al. Adv Mater (2003)
Wiley-VCH [431].)
ARTICLE IN PRESS
that surface interactions are often the governing cylinder walls. That is, weak surface interactions
factor in determining microdomain orientation. should result in a stacked disk structure and strong
Three-dimensional connement, such as in cylind- surface interactions should result in concentric
rical pores, increases the inuence of interfaces even cylinders. Recently, theorists have proposed even
further. Moreover, pore structures are important in more complex morphologies in related systems
both biology and nanotechnology. Pan and cow- [434]. The rst experimental work in this area was
orkers [432] performed Monte Carlo simulations of reported by Russell et al., [435,436] in which porous
symmetric diblock copolymers conned in spheres anodic aluminum oxide (AAO) templates were lled
and cylinders (Fig. 38). These simulations suggested with both cylindrical and lamellar phases of PS-b-
surface forces would induce the lamellae to form PB diblock copolymer via capillary action. This
conformal, layered structures, onion-like in geome- BCP was selected because the strong immiscibility
try, within the limiting volumes. A wider range of of the two blocks maintains microphase separation
parameter space was then investigated with density despite the considerable deformation required to
functional theory to delve deeper into the effect of conformally ll the pores. Asymmetric PS-b-PB
boundary interactions in cylindrical connement displayed cylinders aligning along the pore axes,
[433]. This work proposed, depending on the driven by the preferential wetting of PB on the walls
strength of these interactions, equilibrium structures (Fig. 39). The packing of the cylinders is distorted
composed of microdomains oriented either parallel, from the hexagonal structure observed in the bulk
as previously predicted, or perpendicular to the and in thin lms. The fast Fourier transforms
Fig. 38. Monte Carlo simulations of symmetric BCPs in (a) spherical and (b) cylindrical connement. In both cases, the microdomains
adopt a core-multishell morphology with a periodicity to conform to the conning volume. (Reproduced with permission from J Chem
Phys [432].)
ARTICLE IN PRESS
Fig. 39. TEM cross-sectional images of cylindrical PS-b-PB in pores of different geometry along with the corresponding fast Fourier
transforms. Scale bars: 100 nm. (Reproduced with permission from Xiang et al. Macromolecules (2004) American Chemical Society [435].)
depicted in Fig. 39 reveal that, while hexagonal pores does not match the hexagonal microdomain
packing is present, the symmetry and domain packing. Lamellar structures adopted the concentric
periodicity are different than in the bulk. This cylinder morphology, as expected due to the strong
strain arises because the circular cross section of the surface segregation. However, when the pore
ARTICLE IN PRESS
Fig. 40. Representative TEM images of mesostructures formed inside AAO pores with differing connement dimensions (indicated
underneath each image). (ai) Silver inverted mesostructures prepared by backlling the conned mesoporous silica; (jk) free-standing
mesoporous silica bres; (I) mesoporous silica embedded inside the alumina nanochannels obtained using a focused ion beam.
(Reproduced with permission from Wu et al. Nature Mat (2004) Macmillan Publishers Ltd [438].)
diameter becomes comparable to the lamellar tion, much work has been directed toward under-
period, stacked disks or toroids prevail. Narrow standing the evolution of defects in BCP materials
pores can also impact the morphology of cylindrical and the community is gaining a greater handle on
BCPs, with helical structures observed for pore how to manipulate these defects. New insights into
diameters less than four times the cylinder period the fundamentals of self-assembly are sure to
[437]. More complex nanomaterials can be fabri- emerge in the course of these efforts, and novel
cated by lling AAO pores with a triblock technological applications will be made possible.
copolymer. Such materials can serve as a struc- This review has detailed experimental and theore-
ture-directing surfactant to grow mesostructured tical studies aimed at controlling the alignment of
silica nanowires [438,439]. The nanowires can then, BCPs in the bulk, in thin lms, and in 3-D
in turn, serve as a scaffold to grow inverted connement. Many alignment methods have been
mesostructures (Fig. 40). Using various theoretical successfully applied to different BCP morphologies
methods, a rich collection of unusual morphologies, with varying degrees of success, while other
many of which have not been observed in bulk or methods work only for specic systems. Generally
lm structures, have been predicted for BCPs speaking, methodologies incorporating multiple
conned in cylindrical pores [440442]. elds and merging top-down and bottom-up ap-
proaches lead to the greatest level of control over
7. Conclusions and challenges for the future microdomain structure. As a deeper understanding
of BCP nanostructure is developed, researchers are
Developing methods to control BCP domains is beginning to explore exciting and innovative func-
both a difcult and a valuable challenge. Motivated tions for these materials. One such example is the
both by fundamental scientic questions and an recent report of BCP lamellar distributed Bragg
enormous potential for nanotechnological applica- reectors for organic lasing cavities [443]. This
ARTICLE IN PRESS
review has aimed to provide the reader with both the [15] Hamley IW. Nanostructure formation using block copoly-
motivation driving this eld and a summary of some mers. Nanotechnology 2003;14:R3954.
of the various recent endeavors. It is anticipated that [16] Lazzari M, Lopez-Quintela MA. Block copolymers as a
tool for nanomaterial fabrication. Adv Mater 2003;15:
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Acknowledgment merging bottom-up with top-down processes. MRS
Bull 2005;30:95266.
Use of the Center for Nanoscale Materials was [19] Bang J, Kim SH, Drockenmuller E, Misner MJ, Russell
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Prog. Polym. Sci. 32 (2007) 11521204

Directing the self-assembly of block copolymers

Keywords: Block copolymers; Nanostructures; Nanomaterials; Directed self-assembly; Graphoepitaxy; Alignment

1. Introduction to block copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1153

Tel.: +1 630 252 4580; fax: +630 252 4646.

5.1. Spherical phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1173

Nanotechnology hinges on the ability to create 2.1. Masks and pores

2.2. Nanoparticle synthesis

Domains within BCPs can be used as spatially

2.3. Nanomaterial templating segregate to the boundaries between the BCP

associated with top-down lithography: resolution

The previous section highlights the vast potential

time-lapse observations, supported by dynamic self- 4. Guiding assembly in the bulk

4.1. Spherical phase isoprene-block-styrene) (PS-b-PI-b-PS) triblocks,

Though not as prevalent, non-mechanical eld

achieved by combining multiple, orthogonal exter-

4.4. Other phases

The bicontinuous gyroid phase of BCPs has

Interest in thin lms of BCPs, though they have

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