InvitedPaper

Quantum dot self-assembly in liquid crystal media

Linda S. Hirst*a, Jennifer Kirchhoffa,b, Richard Inmana and Sayantani Ghosha
a
School of Natural Sciences, University of California, Merced, CA 95343
b
Dept. of Physics, Florida State University, Tallahassee, FL 32306
ABSTRACT
In recent years the dispersion and directed assembly of nano-particles in liquid crystal media has proved an interesting
field for investigation and one that may yield new hybrid materials for optical applications and fundamental research. In
this paper, we investigate the dispersion of quantum dots in different liquid crystal phases, looking at aggregation and
pattern formation. Quantum dot self-assembly in liquid crystals is dependent on particle surface properties and
concentration in the liquid crystal medium. By varying these parameters we observe some fascinating structures and
phase behavior using polarized optical microscopy and fluorescence microscopy.
Keywords: Quantum dot, liquid crystal, self-assembly, microscopy, directed assembly, nematic, cholesteric, nanoparticle aggregation.
1.

INTRODUCTION

As a display technology, liquid crystal materials are well known for their anisotropic optical properties and ability to
respond to an applied electric field. This multi-functionality has also been applied to many other technologies beyond the
liquid crystal display with great success and researchers continue to work actively on new and innovative liquid crystal
based technologies. Small particles can be dispersed in liquid crystal media depending on their surface properties and the
study of these mixed systems has been a rich new direction for study over the last decade. Several groups around the
world have been working to understand the interactions of small particles in a liquid crystal solvent1, from metal oxide
nano-particles and carbon nanotubes2,3 on the smallest length-scales, up to larger colloidal particles such as spheres 4,5,
rods6, fluid droplets7 and clay particles8,9.
In this paper we describe the behavior of quantum dots in different liquid crystal phases. Since their discovery in 1983 10
quantum dots have attracted a large amount of interest in the scientific community due to their novel optical properties
and continue to provide inspiration in both fundamental condensed matter physics and for applications in optics and
photonics. Quantum dots are semiconductor nano-crystals, which on illumination at optical wavelengths will emit very
strongly with a narrow emission band correlated to their size. The properties of quantum dots result from their extremely
small size; because the particles are small enough to have discrete energy levels they provide an interesting model
system for quantum phenomena, such as quantum entanglement and coupling. If quantum dots are close enough to each
other their quantum states will combine and this coupling mechanism could lead to new ways to transfer information. By
using a liquid crystal medium as a mechanism to organize quantum dots in a controlled way it may be possible to create
a multifunctional switchable device.
As our motivation in this research is to assemble quantum dots in a controlled way, we have investigated the selfassembly of CaSe quantum dots of different sizes in liquid crystal materials exhibiting the nematic and cholesteric
phases. The size of the quantum dot is an important parameter in this study as it corresponds well to the typical size of a
liquid crystal molecule. This means that when dispersed in the liquid crystal solvent the quantum dots should not have a
significant effect on the director field, although locally the orientation of liquid crystal molecules may be influenced by
their surface properties. In order to investigate this new composite system it is important to learn how the quantum dots
behave when they are mixed with liquid crystal and how the dispersion is affected by parameters such as concentration
and mixing. It is also interesting to characterize the performance of the liquid crystal when the quantum dots are
incorporated and the effects on liquid crystalline properties.
*lhirst@ucmerced.edu; phone 1 209 228 4569 ; http://faculty.ucmerced.edu/lhirst

EmergingLiquidCrystalTechnologiesV,editedbyLiangChyChien,Proc.ofSPIEVol.7618,
76180F2010SPIECCCcode:0277786X/10/$18doi:10.1117/12.848195
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2.

METHOD

Four different liquid crystal materials were used to prepare quantum dot/liquid crystal mixtures. Mixture 1 was prepared
from 40% 5CB (4-cyano-4-n-pentylbiphenyl), the well known room temperature nematic and 60% cholesteric material
COC (cholesteryl oleyl carbonate). Mixture 2 was composed of 90% 8CB (4!-n-octyl-4-cyanobiphenyl) and 10%
AIS179, a chiral ferroelectric material synthesized in the Hird group at Hull University and studied previously by the
authors11,12. Molecular structures for each of the materials can be seen in figure 1. In addition to these mixtures the pure
compound 5CB was used for nematic phase studies. The quantum dots used in this study were purchased from Evident
Technologies. We used CdSe dots varying in size and hence emission wavelength (420, 520, 588 620, and 634 nm).
These ranged in size from ~3-6nm.
Mixtures were prepared by mixing small amounts of quantum dots dissolved in toluene with the liquid crystal materials.
The amounts of toluene added were small enough to not affect the phase boundaries significantly. The quantum dot
solution dissolved readily in the liquid crystal and mixtures were cycled in temperature repeatedly across the isotropic
transition to encourage uniform mixing. Uniformity of the mixtures was verified by polarized microscopic observations
of the isotropic transition across different areas of the liquid crystal between glass plates. In a non-uniform mixture the
temperature for the isotropic transition would vary across the sample. In addition, luminescence from the quantum dots
could be used to also verify uniform mixing.

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Figure 1 Molecular structures and phase sequences for the liquid crystal materials used in this study (a) 5CB (4-cyano-4-npentylbiphenyl ) (b) COC (Cholesteryl oleyl carbonate), (c) 8CB (4!-n-octyl-4-cyanobiphenyl) and (d) AIS179, a chiral
ferroelectric liquid crystal material synthesized by the Hird group at the University of Hull, UK.

Materials were characterized using optical microscopy in a standard liquid crystal device configuration. Briefly, material
is placed between two glass plates, treated to encourage the liquid crystal molecules to lie either parallel (planar
alignment) or perpendicular (homeotropic alignment) to the glass. This sample configuration produces a thin liquid
crystal film that can be tuned in thickness using a spacer film (typically 2-15!m). The glass plates may also include an
indium tin oxide layer (ITO), allowing the application of an electric field perpendicular to the glass across the liquid
crystal film. For observations requiring the application of an electric field, commercial liquid crystal cells (Instec Inc.) of

Proc.ofSPIEVol.761876180F2

thickness 5 !m coated with an anti-parallel planar alignment layer and an indium tin oxide conducting layer were filled
with the liquid crystalline material before being wired for electrical experiments and placed on a Linkham heating stage.
To create an electric field across the liquid crystal films an amplifier and Agilent function generator were used to
produce a 100 Hz square wave.
Polarized microscopy was carried out using a Leica DM2500P upright microscope in transmission mode (Leica
Microsystems Inc., Bannockburn, USA) with a 10x or 20x objective lens. Fluorescence microscopy was carried on the
same microscope without polarizers in reflection mode.
3.

RESULTS AND DISCUSSION

We first examined the effects of concentration on several mixtures of quantum dots with a nematic liquid crystal and
found that good dispersions could only be achieved at concentrations below ~0.01 wt %. This was generally true for all
the different quantum dot sizes investigated. In addition we found that the smaller quantum dots (420nm) were most
likely to form large aggregates in the liquid crystal. Aggregate size was quantified by both dynamic light scattering
measurements and by visual inspection. A mixture was considered to have a good dispersion if very few or no
aggregates were visible to the eye on the optical fluorescence microscope. Light scattering measurements revealed that
sub-optical aggregates were present even if they could not be seen by eye, with a typical size of ~100nm. It is important
to note here that the presence of small aggregates of quantum dots is not necessarily undesirable and that for some
applications involving coupled quantum dots this is actually preferred, especially if the aggregates are nano-scale and
anisotropic. A brief study of mixing revealed that although initially aggregate size at higher concentrations could be
reduced by using a long mixing time, the dispersion was not stable and over time aggregate size would increase after the
mixing was stopped.

Figure 2 Aggregation in the quantum dot/liquid crystal mixtures observed at concentrations above ~0.01 wt % quantum
dots. (a) A close up fluorescence image of an aggregate formed from 420nm quantum dots in the nematic phase (bar =
20!m). (b) Polarized light microscopy image at 100x magnification of the oily streak planar texture in the cholesteric liquid
crystal phase containing 0.011 wt % quantum dots (634nm) (c) the same sample area as shown in (b) imaged with
fluorescence microscopy, showing the localization of quantum dot aggregates in the sample.

In samples with a high concentration of quantum dots ( >0.01 wt %) a background of uniform fluorescence is typically
observed, combined with the presence of larger aggregates. These larger aggregates were found to localize preferentially
at defect rich areas of the liquid crystal texture. This result is not surprising as the presence of large colloidal particles in
the liquid crystal is usually associated with a defect in the texture. The director field must be modified to accommodate
the particle. Figure 2 shows some examples of aggregation in the samples, including a close-up fluorescence image of a

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large aggregate of CdSe quantum dots suspended in the nematic phase, revealing a fairly open fractal-like structure
reminiscent of diffusion limited aggregation (Fig. 2a). Also shown are polarized microscopy (Fig 2b) and fluorescence
(Fig 2c) images of the same area in a cholesteric sample exhibiting macroscopic aggregation. The smallest quantum dots
used in this study (420nm) were most likely to aggregate, 520 and 620nm QD gave reasonably good dispersions at <0.01
wt %.
At lower concentrations of quantum dots in liquid crystal (<0.01 wt% ) we observed some interesting effects on the
liquid crystal phase itself. Figure 3 shows an example of these effects. Most obviously we noticed a change in pitch for
the cholesteric phase in our mixture, with a clear change in reflection colors from green (fig 3a) to red (fig 3d). This
effect has been previously observed by Mitov et al13, where they showed that platinum nano-particles can be assembled
in cholesteric defects and observed that the cholesteric pitch was increased in the presence of nano-particles. In addition
to this observation we also observed that the quantum dots slightly decrease the threshold field for the Freedericksz
transition in the cholesteric phase, although this is a topic for future investigation.

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Figure 3 Optical microscopy images of the liquid crystal cholesteric phase in a planar device geometry. Images a) c)
show the cholesteric phase before (a), during (b) and after (c) the application of a 2V/!m square wave 100Hz electric field.
(d) (g) show the same material, but with the addition of 634nm CdSe quantum dots at a concentration of 0.009 wt %. (d)
and (e) represent the material before the application of the electric field, (d) being a polarized optical microscope image and
(e) a fluorescence microscope image. (f) and (g) show the material under polarized light microscopy during and after the
field application.

Nematic, cholesteric and smectic liquid crystals all have distinctive and often regular defect textures so as a strategy to
produce ordered arrays of quantum dots we investigated the correlation between liquid crystal textural features and
quantum dot localization. Unaligned nematic liquid crystals exhibit distinctive brush textures. These appear as dark
lines in the material between crossed polarizers as the director rotates by 180 over a short distance. A typical nematic
schlieren texture can be seen in figure 4a. The cholesteric phase can exhibit a fingerprint texture (seen in figure 4c) as
the axis of the cholesteric helix lies parallel with the glass. In this geometry the director rotates about an axis parallel
with the glass and thus the birefringence of the material varies in intensity from dark to light, the maximum being when
the molecules are parallel with the glass and the minimum birefringence when they are perpendicular with the glass.

Proc.ofSPIEVol.761876180F4

Correlations between liquid crystal defects in these two phases and quantum dot localization were investigated by
comparing polarized optical microscopy images (liquid crystal birefringence texture) with fluorescence microscopy
images (showing quantum dot emission and therefore localization). This technique of using a microscope with both
polarized light and fluorescence imaging allows us to examine liquid crystal texture and quantum dot distribution in the
same area.
As can be seen in figure 4, we observed some surprising results. Previous work by Mitov et. al 13. on mixtures of
platinum nano-particles with a polymerizable cholesteric material had indicated that we should expect to see a quantum
dot pattern well matched with the defect texture. In fact we observed no apparent correlation between the birefringence
texture and the quantum dots. However we did observe distinctive distributions of quantum dots in the material. Figure 4
demonstrates the overlay of quantum dot distribution and liquid crystal texture in the nematic and cholesteric phases.
These images were taken at room temperature (nematic phase) and 42C (cholesteric phase, Mixture 2). It is clear that
although a direct correlation between the patterns was not observed, there is an important role being played by the liquid
crystal phase in ordering the quantum dots. In both cases bands or ribbons of more concentrated quantum dots were
observed (figs. 4b,e) running through the material.

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Figure 4 Polarized and fluorescence optical microscopy images of quantum dot/liquid crystal mixtures in the nematic
phase for pure 5CB at 100x magnification: (a,b and c) and the cholesteric phase for the cholesteric mixture (fig 1): (c, d and
e). Each set of images represents the same sample area. Image (a) is a polarized microscopy image of the classic nematic
liquid crystal defect texture with (b) being fluorescence imaging of the same sample area showing quantum dot distribution.
(c) shows a superposition of the nematic texture with the overall quantum dot distribution marked by lines to demonstrate
where the quantum dots are with respect to the liquid crystal texture. Lines are intended to guide the eye. Images (d-f)
represent the corresponding images for the cholesteric phase in the characteristic fingerprint texture.

At this point in the investigation we can only speculate on the mechanisms for this ribbon pattern formation, as more
comprehensive characterization must be carried out on this system. It has been observed that the ribbon pattern in the

Proc.ofSPIEVol.761876180F5

cholesteric phase forms on cooling from the isotropic phase. If the material is cooled further into a smectic phase, this
pattern disappears and on reheating does not reform unless the material is reheated to isotropic and cooled again. One
possible theory is then that the pattern forms as a result of cooling from the isotropic phase. When a liquid crystal phase
nucleates from the isotropic phase at the transition point quantum dots may migrate to remain in the isotropic phase until
the transition is complete. Due to their small size it could be more favorable for the particles to remain in the more
disordered regions of the sample. It is possible that this migration to the remaining isotropic regions as the transition
occurs could lead to a network of quantum dot rich areas in the sample, leaving an image of the growth pattern of the
liquid crystal phase from the isotropic.
Controlled pattern formation of quantum dots and other nano-particles will be a fascinating area of research for the
future as the properties of quantum-scale particles become more important for device applications. In this paper we have
shown that liquid crystal phases have the potential to assemble quantum dots based on the liquid crystal phase in
question, although the mechanisms for this assembly are still not clear. In order to achieve the goal of controlled
assembly, detailed studies of quantum dot dispersion in liquid crystal media must be carried out to ascertain the
aggregation characteristics of different nano-crystals as a function of concentration, particle size and surface properties.

4. ACKNOWLEDGEMENTS
The authors would like to acknowledge generous funding from the National Science Foundation, through an NSF
CAREER award (DMR BMAT #0852791). Additional support was provided by the School of Natural Sciences, at the
University of California, Merced and by the Center for Materials Science and Technology (MARTECH) at Florida State
University. We would also like to thank Prof. Mike Hird at the University of Hull, UK for providing liquid crystal
materials.

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