full papers

Electron-beam lithography

A Simple Top-Down/Bottom-Up Approach to Sectored,

Ordered Arrays of Nanoscopic Elements Using Block
Copolymers
Soojin Park, Ozgur Yavuzcetin, Bokyung Kim, Mark T. Tuominen, and Thomas
P. Russell*

A top-down/bottom-up approach is demonstrated by combining electronbeam (e-beam) lithography and a solvent annealing process. Micellar arrays
of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) with a high
degree of lateral order can be produced on a surface where sectoring is
defined by e-beam patterning. The e-beam is used to crosslink the block
copolymer (BCP) film immediately after spin-coating when the BCP is
disordered or in a highly ordered solvent-annealed film. Any patterns can be
written into the BCP by crosslinking. Upon exposure to a preferential
solvent for the minor component block followed by drying, cylindrical
nanopores are generated within the nonexposed areas by a surface reconstruction process, while, in the exposed areas, the films remain unchanged.
Nickel nanodot arrays can be placed over selected areas on a surface by
thermal evaporation and lift-off process.

1. Introduction
Controlling the lateral placement of nanometer-sized
objects into arbitrary arrangements is important for the
fabrication of functional nanostructured materials for use in
optical, optoelectronic, and magnetic storage devices.[15] The
self-assembly of block copolymers (BCPs) into aligned, highly
ordered arrays of nanoscopic domains makes them ideal
candidates as templates and scaffolds for the fabrication of
nanostructured materials. Demands become even more
stringent for addressable media wherein the exact location
of each nanoscopic object must be precisely controlled over
large lateral length scales.[1,68] To this end, top-down
approaches, like photolithography, electron beam (e-beam)
[
] Dr. S. Park, B. Kim, Prof. T. P. Russell
Department of Polymer Science and Engineering
University of Massachusetts, Amherst, MA 01003 (USA)
E-mail: russell@mail.pse.umass.edu
O. Yavuzcetin, Prof. M. T. Tuominen
Department of Physics
University of Massachusetts, Amherst, MA 01003 (USA)

DOI: 10.1002/smll.200801573

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Keywords:






block copolymers
lithography
micelles
nanodots
nickel

lithography, X-ray lithography, and contact molding processes, have been used to pattern surfaces on microscopic
length scales so that the patterning can be used to guide the
self-assembly of the nanoscopic elements laterally.[912]
Graphoepitaxy has been used to confine nanostructured
materials within topographic constraints produced on a
surface by photolithographic or etching procedures. Using a
BCP composed of a high-resolution photoresist, in particular
poly(4-hydroxystyrene) with poly(a-methylstyrene), Du et al.
were able to control the spatial location of BCP microdomains
by a top-down deep UV lithographic process.[13] Uniform
arrays of nanoscopic cylindrical microdomains were produced
over large areas by this simple fabrication processes. Glass
et al., on the other hand, used e-beam lithography to pattern
polystyrene-block-poly(2-vinylpyridine) micelles in selective
areas.[5,14] The immobilization of micelles within the e-beam
exposed regions occurred due to a crosslinking of the micelle
corona by the electron beam. These techniques and others
provide elegant routes in selectively placing nanoscopic
domains over well-defined areas on insulating or conducting
surfaces. Meister et al. demonstrated a novel way to combine
top-down and bottom-up approaches where nanopatterned
surfaces, generated by depositing attoliter quantities of a
liquid on a surface with a high lateral accuracy using a

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Arrays of Nanoscopic Elements Using Block Copolymers

cantilever-based nanoscale dispenser, were used to direct the

lateral distribution of BCP micelles.[15] However, the control
over the lateral ordering of the micelles in these studies was
not suitable for device applications and the area over which
the patterning can be perform is limited by the scanning area
of the dispenser. Solvent annealing provides one route to
overcome many of the limitations encountered by lithographic
or scanning force microscopy-based techniques in controlling
the orientation and lateral ordering of BCP microdomains or
micelles in thin films. The preparation of BCP micellar films
under various solvent annealing conditions has been reported
by several groups to control the size and lateral ordering of
arrays of BCP micelles.[1619] The presence of a solvent
enhances the mobility of the BCP chains and micelles,
allowing a redistribution of the BCP chains between micelles
on the solid substrate and removal of defects in the lateral
packing of the micelles. The highly ordered hexagonal arrays
that result from the solvent annealing extend over very large
lateral areas and have the potential of generating addressable
media suitable for addressable storage applications.
By combining a top-down e-beam lithography approach
with a bottom-up solvent annealing process, we show that
micellar arrays of polystyrene-block-poly(4-vinylpyridine)
(PS-b-P4VP) with a high degree of lateral order can be
produced on a surface where sectoring is defined by the
e-beam patterning. Unlike other processes, the e-beam was
used to crosslink the BCP film immediately after spin-coating
when the BCP is very disordered or in a highly ordered solvent
annealed film (Figure 1a). Both line and polygon patterns can
be written into the BCP by crosslinking. Equally important is
that the crosslinked BCP consists of the same components as
the BCP ordering with the areas defined by the e-beam
crosslinking and, as such, represents lateral constraints where
the interactions with the blocks of the BCPs are balanced. In
addition, the surface of the film remains essentially flat with
only a very slight depression in the exposed areas, resulting
from the volume contraction associated with crosslinking.
Upon exposure to a solvent that is a good solvent for the minor
component block followed by drying, cylindrical nanopores
are generated within the nonexposed areas by a wellestablished reconstruction process, while, in the exposed
areas, the films remained unchanged, since crosslinking
suppresses swelling (Figure 1c). Using a template prepared
in this manner, arrays of nickel (Ni) nanodots could be placed
over selected areas on a surface by a thermal evaporation and
lift-off process (Figure 1d).

2. Results and Discussion

Figure 1. Schematic illustration for the fabrication of nanoscale patterns from a combination of top-down and bottom-up approaches.
a) Highly ordered hexagonal arrays obtained from a solvent annealing
process. b) E-beam exposed regions can be crosslinked. c) Nanopores
can be produced in e-beam unexposed regions by a surface reconstruction process. d) Metal-dotted arrays can be obtained by metal
evaporation, followed by a lift-off process.

Amphiphilic BCPs like PS-b-P4VP form uniform micelles

in solvents that are preferential for one block. Here we used
toluene, which preferentially solvates PS, the major component block. The PS chains form a corona around a core of the
insoluble P4VP block. The diameter and separation distance
of the micelles can be tuned by the molecular weight of
the BCPs, the interactions between the polymer blocks, and
the relative solubility of the blocks in the solvent.[20]

A micellar solution of PS-b-P4VP in toluene (0.5 wt%)

was spin-coated onto a silicon substrate. The PS-b-P4VP
used in this study was purchased from Polymer Source
(number-average molecular weight MnPS 47.6 kg mol1,
MnP4VP 20.9 kg mol1, molecular weight distribution Mw/
Mn 1.14). As-spun micellar films have a broad size distribu-

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T. P. Russell et al.

Figure 3. Height mode SFM images (1.5 mm  1.5 mm) of solvent

annealed (a) and reconstructed films (b). After surface reconstruction,
nanoporous structures can be generated without changing the separation distance.

Figure 2. Height-mode SFM images of PS-b-P4VP films reconstructed in

ethanol after e-beam exposure in a) 10, b) 11, c) 12, d) 14, e) 16, and
f) 18 nC cm1 doses. Scale bars are 100 nm.

tion of domains, resulting in very short-range hexagonal

ordering as shown previously.[19] When the as-spun micelle
films were exposed to tetrahydrofuran (THF, Aldrich, 99.5%)
vapor, which is a good solvent for both PS and P4VP, at room
temperature for 3 h, the lateral ordering of the micelles was
markedly enhanced, as shown in the scanning force microscopy (SFM) image in Figure 2a. The solvent annealed PS-bP4VP films are characterized by a hexagonal array of
nanoscopic domains with an average nearest-neighbor dis-

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tance of 43.3  2.5 nm. When the well-developed PS-b-P4VP

micelles were immersed in ethanol, a good solvent for P4VP
and a nonsolvent for PS, for 20 min, a reconstruction of the film
occurred, producing a highly oriented array of nanoscopic
pores (Figure 1b) having an average separation distance equal
to that seen in the film before exposure to ethanol. As shown
previously, this solvent reconstruction of BCP films can be
used to generate nanoporous templates without removing
either component of the BCP while preserving the lateral
order.[21,22] By immersing the films in ethanol, the P4VP is
solvated while the glassy PS matrix remains intact, and, upon
drying, the P4VP is deposited on the surface of the film,
leaving the a porous film.[15,2123] This process, of course, is
operative only for films with thicknesses L0/2 thick, where L0
is the equilibrium period of the BCP. The reconstructed film
was floated onto the surface of an HF buffer (1 wt%) solution,
then transferred to a silicon substrate, as reported previously,[24] to ensure the penetration of the pores through the
film.
E-beam lithography (JEOL 6400 scanning electron
microscope (SEM) and NPGS system) was used to write on
a thin film of PS-b-P4VP having long-range lateral ordering of
the micelles so as to selectively crosslink areas of the BCP.
Upon exposure to ethanol, a good solvent for the minor
component, P4VP, the exposed crosslinked areas remained
unchanged, while a nanoporous film was produced in the
nonexposed area. The back scattering of electrons causes the
exposed regions to be larger than the size of the beam, and
the line edge roughness is comparable to that seen with
standard photoresist materials.[25]
The e-beam exposure was varied from 10 nC cm1 to 18 nC
1
cm . Figure 3 shows the SFM height images of reconstructed
films after e-beam exposure for six different doses. To
investigate the effect of e-beam dose on line width and shape
of crosslinked regions, an equilateral triangle of side length
500 nm was prepared. As shown in Figure 3, the single line
exposures of 10, 11, 12, 14, 16, and 18 nC cm1 gave line widths
of 96, 100, 108, 132, 149, and 202 nm, respectively. As the line
exposure increases, the line width and number of crosslinked
micelles increases while the number of nanopores decreases,
as shown in plot of Figure 3g. The squares and triangles in the
figure represent the number of crosslinked micelles and
nanopores as a function of e-beam dose, respectively. When

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Arrays of Nanoscopic Elements Using Block Copolymers

Figure 5. BCP microdomain arrays having square, circular, and triangular patterns. At certain e-beam dose conditions, a sharp boundary
between crosslinked micellar and nanoporous structures was seen in
the height-mode SFM images (1.5 mm  1.5 mm).

Figure 4. Height-mode SFM images (1.5 mm  1.5 mm) of BCP microdomain arrays prepared from an e-beam dose and reconstruction
process. Line widths of a) 35, b) 42, c) 60, and d) 65 nm were obtained
from different e-beam doses.

the e-beam dose exceeded 18 nC cm1, no nanopores were

observed within the triangular region, indicating that all the
BCPs were crosslinked. It should be noted that the line width is
very sensitive to the exposure dose, which can further be used
to control the density of pores on the surface.
Figure 4 shows SFM images of reconstructed films after
e-beam exposure at four different doses. The single line
exposures of 2, 4, 7, and 8 nC cm1 gave line widths of 35, 42,
60, and 65 nm, respectively. The P4VP blocks were not
sufficiently crosslinked at the lowest dose (Figure 4a), while at
doses higher than 2 nC cm1, complete crosslinking of the BCP
occurred, as shown in Figure 4bd. A film that was exposed to
a dose of 4 nC cm1 with a line width less than the separation
distance between neighboring micelles shows a micelle array
with one row of crosslinked domains (Figure 4b). The line
widths obtained at higher doses were greater than the
separation distance between the micelles and 2 rows of
the crosslinked micellar domains could be produced within
sharply defined boundaries (Figure 4c and d). It should be
noted that the well-developed films exposed to the e-beam
can be immobilized in an appropriate solvent, and line
arrangements of nanopore locations can be precisely controlled.
Patterns incommensurate with the hexagonal packing of
the micelles, like squares, circles, and triangles, can be
generated in a similar manner. This was done at three different
e-beam line doses (2, 4, and 7 nC cm1, Figure 5). At the lowest
dose, the boundary between the patterned and unpatterned
regions is not sharp (top row of shapes in Figure 5), since the
films are only lightly crosslinked. At high doses the boundary
between exposed and unexposed regions is sharp (bottom two
rows in Figure 5). For patterns with straight sides, like squares
and triangles, the crosslinked micelle patterns follow the
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written e-beam pattern, while for patterns that have curved

sides, like a circular pattern, polygonal patterns result.
Unlike other processes, the e-beam was used to crosslink
the BCP film immediately after spin-coating from a neutral
solvent for both blocks, such as N,N-dimethylformamide,
when the BCP was very disordered. When the as-spun film was
exposed to a dose of 8 nC cm1, the exposed regions were
completely crosslinked. It should be noted that, over the
course of 3 h, even crosslinked BCP thin films can migrate
during solvent annealing in THF vapors, which are slightly
selective for PS, and, therefore, it is difficult precisely define a
confinement area. When the films were exposed to THF/
cyclohexane (70:30, v/v) for 4 h, followed by immersion in
ethanol for 20 min, the e-beam exposed regions unchanged
(Figure 6). The lattice spacing between two micelles in the
direction parallel to the e-beam pattern is equal to the original
lattice spacing (d 37.6 nm) observed on a flat substrate, as
shown in Figure 2a. When the line width is incommensurate

Figure 6. SFM image of BCP films annealed in solvent vapor and

followed by a surface reconstruction process after crosslinking the BCP
film immediately after spin-coating. Scale bar is 100 nm.

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ing, e-beam writing, and a surface reconstruction process.

When the PS-b-P4VP thin films with a high degree of lateral
order were exposed to the e-beam, selected areas of the BCP
were immobilized, and arrays of nanoporous structures could
be produced within areas with arbitrary patterns by a solvent
reconstruction. From highly oriented nanoporous templates,
Ni nanodot arrays were produced while maintaining separation distance and diameter of the nanoporous template. This
method should be applicable to other BCPs, provided
solvation conditions for the different blocks can be maintained, and to the deposition of any material by evaporation.

Figure 7. SEM image of Ni dotted arrays obtained from Ni deposition

and a lift-off process using periodic line patterns. The separation
distance and diameters of the Ni dots are similar to the original
templates. Scale bar is 100 nm.

with the ideal period, d, the periodicity of the block copolymer

micelle is compressed or expanded to fit within the patterns.
These results are in agreement with previous results using
cylinder or sphere-forming block copolymers.[2628] This
method opens a new route to the preparation of patterns
having neutral walls, since disordered PS-b-P4VP films are
crosslinked by e-beam lithography over arbitrary patterns.
The quality of the film is the same, whether the film is e-beamexposed directly after spin-coating or after the film was solvent
annealed. By exposing the film before annealing, the exposed
crosslinked areas produced walls composed of a mixture of
both components, making the interactions with the blocks of
the copolymer the same, that is, the walls are effectively
neutral.
BCP thin films with a high degree of lateral order within
the submicrometer-sized patterns can be used as templates for
deposition. Here, Ni nanodot arrays were prepared by the
thermal evaporation of Ni followed by a lift-off process. BCP
thin films obtained from solvent annealing, e-beam writing
(8 nC cm1 dose), and a surface reconstruction process were
used as templates for the preparation of arrays of Ni nanodots.
Figure 7 shows an SEM image of a Ni nanodot pattern
prepared in this manner after lift-off with chloroform (CHCl3,
Fisher). Before Ni evaporation, the P4VP wetting layer was
removed by oxygen plasma (TRION Technology, applied
power: 60 W, etching time: 10 s). Ni was thermally evaporated
onto the template at a pressure of 6  106 Torr to a nominal
thickness of 13 nm at a rate of 0.01 nm s1, as measured with a
quartz crystal microbalance. Finally, the BCP template was
removed by ultrasonication in CHCl3 for 3 min. Ni dotted
arrays having an average separation distance of 43 nm, which
is identical to that of original template, were produced. This
process should be applicable to any material that can be
thermally evaporated.

3. Conclusions
We have demonstrated a simple method to generate
patterned arrays of nanoscopic objects using solvent anneal-

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Acknowledgements
This work was supported by the U.S. Department of Energy
(DOE), the NSF supported MRSEC and NSEC (CHM) at the
University of Massachusetts Amherst. The partial support of
this work by Seagate Technologies is gratefully acknowledged.

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2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Received: October 22, 2008

Revised: November 20, 2008
Published online: February 2, 2009

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