Invited Paper

Self-assembly in nematic colloids

Igor Muševič*a,b , Miha Škarabota, Miha Ravnikb, Uroš Tkaleca, Igor Poberajb, Dušan Babičb and
Slobodan Žumera,b
a
J. Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia
b
Faculty of Mathematics and Physics, University of Ljubljana, Jadranska 19, 1000 Ljubljana,
Slovenia

ABSTRACT

The ability to generate regular spatial arrangements of particles on different length scales is one of the central issues of
the "bottom-up" approach in nanotechnology. Current techniques rely on single atom or molecule manipulation by the
STM, colloidal particle manipulation by laser or optoelectronic tweezers, microfluidics, optofluidics, micromanipulation
and classical lithography. Of particular interest is self-assembly, where the pre-determined spatial arrangements of
particles, such as 3D photonic crystals, could be realized spontaneously. Dispersions of particles in liquid crystals show
several novel classes of anisotropic forces between inclusions, which result in an amazing diversity of self-assembled
patterns, such as linear chains and 2D photonic crystals of microspheres. The forces between the particles in nematic
colloids are extremely strong and long-range, resulting in several thousand times stronger binding compared to the
binding in water based colloids. The mechanisms of self-assembly in nematic colloids are discussed, showing this is a
novel paradigm in colloidal science, which can lead to new approaches in colloidal self-assembly for photonic devices.

Keywords: photonic crystals, micromanipulation, laser tweezers, colloids, nematic liquid crystal

1. INTRODUCTION

Transport and self-assembly of materials on different length-scales are issues of great current interest due to their
possible applications in nanotechnology and photonics. In order to assemble or self-assemble small objects into 2D and
3D complex structures, much effort has been devoted to the study of novel forces between objects that are not of the
electromagnetic origin. These are, for example, responsible for the stability of classical colloidal systems based on water
dispersions of particles and play an important role in everyday technology including food production, paint, etc. Liquid
crystals exhibit a new class of forces between objects, which are the consequence of the spontaneously broken rotational
symmetry of liquid crystals and long-range orientational order [1]. These forces are the "structural forces", as they are
caused by the intrinsic "structure" of an ordered fluid [2]. The structural forces between inclusions in nematic liquid
crystals give rise to interesting self-assembly processes and induce growth of unique self-assembled structures such as
linear chains [3, 4], 2D hexagonal arrangements of particles at interfaces [5, 6], regular arrays of defects [7], anisotropic
clusters [8], cellular structures [9], and even long-range ordered 2D structures in thin nematic layers [10]. These studies
have shown, that a rich variety of structural forces in the nematic liquid crystals could be used to design novel materials
and devices, such as, for example, photonic crystals [11, 12, 13, 14, 15, 16, 17].

Liquid Crystals and Applications in Optics, edited by Milada Glogarova, Peter Palffy-Muhoray, Martin Copic
Proc. of SPIE Vol. 6587, 658704, (2007) · 0277-786X/07/$18 · doi: 10.1117/12.724547

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 Recently we have reported [10] the directed self-assembly of two different types of 2D colloidal crystals using
micrometer sized silica spheres in a thin layer of nematic liquid crystal. We have used micron-sized glass particles with
homeotropic boundary conditions, which were dispersed in the nematic liquid crystal. Depending on the thickness of the
planar nematic cell, dipolar colloids were observed at larger thickness of the cell as quadrupolar colloids at cell
thickness comparable to the diameter of the colloidal particles. We have observed that the colloidal particles not only
form linear dipolar chains or quadrupolar kinked chains, but also long-range ordered 2D crystals. These are strongly
bound, with binding energies of the order of 1000 kBT per micrometer size particle. Here we review our recent work on
directed self-assembly of nematic colloidal crystals.

2. MATERIALS AND METHODS

2. 1. Sample preparation
Silica colloidal particles have been used in the experiments. The distribution of the diameters of the colloidal particles
has been determined by imaging a large number of colloidal particles under an optical microscope, followed by particle
size analysis. The mean diameter of the colloidal particles was 2R = 2.32 ± 0.02 µm. The surfaces of the particles have
been coated with a monolayer of N,N-dimethyl-N-octadecyl-3-aminopropyltrimethoxysilyl chloride (DMOAP) that
induces a very strong homeotropic surface anchoring of the nematic liquid crystal 5CB (4-cyano-4’-n-pentylbiphenyl).
The colloidal particles were first dispersed in a 0.5 % water solution of DMOAP for several minutes. Then, the particles
were rinsed with distilled water and dried. Coated particles were introduced in the 5CB at a concentration of several
percents. The nematic dispersion was further introduced in glass cells with planar surface anchoring. The surfaces of the
glass were treated with a polyimide PI 5291 (Brewer Science) that was rubbed to induce good parallel alignment of
5CB. The cells were prepared using mylar spacers on one edge and no spacer on the other edge. In this way, wedge-like
cells were obtained, with thickness varying from 1 µm to 6 µm. The local thickness of the cell was measured with a
spectrophotometer as a function of the separation from the thinnest part, and was known to better than 100 nm at a
given position. After the nematic dispersion of colloidal particles was introduced in the wedge-type cell, we have
observed dipolar director field around colloidal particles above the threshold thickness of 3.5 µm. Here, the dipolar
colloidal particle is formed by the particle itself, representing the radial topological defect and the second topological
defect, which is of hyperbolic type and is located close to the colloidal particle. Together, they form a topological
dipole. For smaller cell thickness, the dipolar field around the colloidal particles was transformed into the quadrupolar,
Saturn-like arrangement. Here, the hedgehog topological point defect "opens" into a small ring, encircling the colloidal
particle.

2. 2. Experimental set-up and procedures

Laser tweezers have been used to position colloidal particles [10] and assist their assembly into stable 2D structures. We
have used a multi-trap laser tweezers setup built around an inverted microscope and a CW diode-pumped solid-state
laser at 1064 nm as a laser source. An acousto-optic deflector (AOD), driven by custom made electronics controlled by
a PC was used for trap moving. A beam expander was used to match the laser beam to the AOD aperture and some
additional optics was used to image the pivotal point of the AOD onto the entrance pupil of the water immersion
microscope objective (Zeiss, IR Achroplan 63/0.9W). The maximum laser power of a diffraction limited beam in the
sample plane was up to 64 mW. The temporal position of the colloidal particles was video-monitored using an optical
microscope and image capture. In an off-line analysis the colloidal trajectories were further analyzed [18]. The position
of the particle center of gravity was determined by video-analysis of the captured frames with an accuracy of ~ 5 nm.
Having the recorded time-dependence of the separation between the particle and the laser focus, it was possible to
v
restore the effective elastic pair potential acting on the particle. Following the Stokes law, F = 6πR eff η dr dt , we can

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 calculate the force between the light focus and the silica particle [19]. Finally, by integrating the force over the
separation the interaction energy can be calculated .
3. RESULTS AND DISCUSSION

3. 1. Directed self-assembly of dipolar colloidal particles

At cell thickness, larger than the critical thickness of 3.5 µm for 2.32 µm colloidal particles, the homeotropic boundary
condition at colloidal surfaces gives rise to dipolar-like configuration of the director field around the particles. It has
been observed that the dipolar particles spontaneously assemble into dipolar chains, oriented along the director in a
planar cell [3, 4]. Figure 1a shows an example of a dipolar chain assembly, where the colloidal particle was positioned
using laser tweezers in the vicinity of the chain and released. From the sequence of images one can determine the
trajectory of the dipolar particle, determine the viscous drag force and therefore also the structural force of attraction
[19], which is presented in Figure 1b. Similar to the structural force that binds a single pair of two parallel colloidal
dipoles, the attraction force of a single colloidal particle to a dipolar chain shows 1 r 4 separation dependence [20,21].
By integrating the force with respect to particle translation, the binding potential of the order of 5000 kBT is obtained, as
shown in Figure 1c.

a)

b)
11111 nil c) I I
____ I °I I

5
-30J0.

0o -40J0.
-50J0. d2
I
I I I
10 2 4 6 8 10
Separation [pm] Separation [pm]

Figure 1: (a) A sequence of video-frames, where a silica microsphere of 2.32 µm diameter, dispersed in a nematic
liquid crystal, is attracted to the chain of microspheres. Note that each microsphere has a small dark spot, which is the
"hedgehog" topological defect. (b) The force of attraction of the microsphere, as calculated from the top sequence. (c)
The corresponding binding potential.

The structural forces for a single dipolar colloidal particle, approaching the colloidal chain laterally, depend strongly on
the orientation of the isolated dipolar colloidal particle and the dipoles in the chain. This is illustrated in Figure 2, where
two different sequences of images are shown. In the upper sequence of images, Figure 2a, the orientation of the isolated

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 dipole is in the same direction as the orientation of the dipoles in the closest dipolar chain. This can be resolved by
looking at the position of the small dark spots (i.e. hedgehog defects) near the colloidal particles, which are in both
cases at the bottom of the particles. This means the topological dipoles are parallel to each other and as one can see from
sequence in Figure 2a, the dipole is repelled from the neighboring chain. The opposite is observed, if the orientation of
the isolated dipole is reversed, as shown in Figure 2b. In this case, the isolated dipole is pointing "up", the dipoles in the
first neighboring chain are pointing "down" and the dipole is attracted to the chain.

aggj. urn

b)IJJJj i11JI i1I1J

c) d) 2. 11111 I
2!
1.
0• __
a)
-1.
-3.
• • •
i i 14 110112 14
Separation [jam]
Separation [jim]

Figure 2: (a) Repulsion of an isolated dipolar colloidal particle from the first neighboring dipolar chain. Note the
orientation of "hedgehog" defects (dark spots), which are in both cases pointing "down". (b) If the orientation of the
isolated dipole is reversed, it is attracted to the chain. The time separation between individual images in (a) and (b) is 14
seconds. (c) The force and (d) the potential of an isolated dipolar colloidal particle, as calculated from sequences in (a)
and (b). The upper curves (squares) correspond to repulsion, the lower curves (circles) correspond to attraction.

The calculated forces of repulsion and attraction are shown in Figure 2c and are of the order of several pN at a typical
separation of several micrometers. The corresponding binding potential is extremely strong and is of the order of 3000
kBT for a 2.32 µm silica particle. This is typically three orders of magnitude stronger compared to water-based colloids
and results in extremely robust dipolar colloidal structures. As the dipolar colloidal particles are attracted to a
neighboring dipolar chain if their dipoles are anti-parallel, it is possible to assemble 2D dipolar colloidal crystals, as the

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 one, shown in Figure 3. The dipolar colloidal crystals are very stable and can be transported using laser tweezers over

-It.
micrometer distances without disrupting the crystalline order.

d\-
jIJ
I A.A

Figure 3: An example of a 2D nematic colloidal crystal, assembled by using laser tweezers.

3. 2. Self-assembly of quadrupolar colloidal particles.

For the cell thicknesses below 3.5 µm, the homeotropic boundary condition at colloidal surfaces can no longer sustain
the dipolar-like configuration of the director field and changes to quadrupolar, Saturn like configuration [1, 22]. Similar
to dipolar chains, observed for dipolar colloidal particles, the quadrupoles self-assemble into chains [23]. However, in
contrast to linear dipolar chains, the quadrupoles assemble into kinked chains, which grow in the direction,
perpendicular to the director of the planar cell. This is illustrated in Figure 4, where several randomly assembled chains
are shown.

r
ac4

1I
I
Figure 4: If the thickness of the planar cell is comparable to the diameter of colloidal particles, the symmetry of the
nematic distortion around individual colloidal particle is quadrupolar. Quadrupolar colloidal particles attract each other

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 at an angle, which results in randomly kinked chains, oriented perpendicular to the nematic director of the planar cell.

Similar to the dipolar nematic colloids, the quadrupolar nematic colloids also self-assemble into 2D colloidal crystals.
This is formed by stacking a set of kinked quadrupolar chains, which can rearrange in an almost hexagonal structure
with a more symmetric distribution of Saturn ring defects, as shown in Figure 5. A directed assembly of an isolated
quadrupolar colloidal particle into unoccupied corner position together with corresponding structural force and potential
is shown as well. In comparison to dipolar 2D nematic colloidal crystals, the quadrupolar 2D crystallites are much more

•0*0*•
fragile and susceptible to external stimuli, such as liquid flow, etc.

b) c)
01
9
of
-200

aa) -400
2
1-600
-800
-3 ci'
2 3 4 5 •6 2 6
Sepaation [pm] Separation [pm]

Figure 5: Directed assembly of quadrupolar colloidal particles into a 2D nematic colloidal crystal. (a) Using laser
tweezers, the colloidal particle was positioned close to the corner of an already formed crystallite and released. Directed
attraction into unoccupied corner due to the structural force is clearly observed. The time difference between individual
frames was 1 second. (b) The attraction force of a single colloidal quadrupolar particle to the already formed 2D
quadrupolar crystallite. (c) The binding energy of the colloidal particle as a function of its separation from the
unoccupied corner position.

4. CONCLUSION

We have presented a clear experimental evidence that stable and long range ordered nematic colloidal crystals can be
assembled in thin nematic layers. Unlike forces that are responsible for long range order of colloids in isotropic host
liquids, the forces that bind together the nematic colloids are of structural origin and therefore much richer in the sense

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 of their anisotropy. Two different types of 2D nematic colloidal crystals have been observed in our experiments, with
quadrupolar and dipolar symmetry, respectively. In both cases, the binding mechanism is the same and represents a fine
balance between two basic mechanisms: (i) the colloids minimize the volume of an elastically distorted nematic by
approaching each other and thus sharing topological defects, i. e. regions of distortion, with each other; and (ii) at close
separations between colloidal particles, repulsive structural forces are generated due to strong spatial variation of the
nematic order. A delicate balance between these two effects governs the positional and orientational ordering of nematic
colloidal crystals.
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