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Solar Energy Materials & Solar Cells 93 (2009) 329333

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Solar Energy Materials & Solar Cells


journal homepage: www.elsevier.com/locate/solmat

Electrically switchable chromogenic materials for external glazing


Daniela Cupelli a, Fiore Pasquale Nicoletta a,, Sabrina Manfredi b,
Giovanni De Filpo b, Giuseppe Chidichimo b
a
Dipartimento di Scienze Farmaceutiche, Universita` della Calabria, 87036 Rende (CS), Italy
b
` della Calabria, 87036 Rende (CS), Italy
Dipartimento di Chimica, Universita

a r t i c l e in fo abstract

Article history: The development of chromogenic materials is important for their potential applications as electrically
Received 3 July 2008 adjustable or thermally self-adjusting light and heat lters in the external glazing of buildings. Recently,
Accepted 12 November 2008 we have reported our investigations on electrolyteliquid crystal dispersions, which show independent
Available online 21 December 2008
electro-optical and electrochromic properties characterized by fast bleaching times. Nevertheless, for
Keywords: the external glazing of buildings, it is recommended to have a transparent off state, which turns opaque
Smart windows upon application of the external eld. In this paper, we present our efforts to homeotropically align by
Electrochromism rough surfaces uid mixtures of a low molecular mass liquid crystal with a negative dielectric
Liquid crystals anisotropy, a liquid crystalline monomer, and electrolyte molecules in order to obtain transparent lms
PDLC
after a polymerization process. Upon application of an ac electric eld, the device becomes opaque and
Chromogenics
if a dc eld is added, the cell changes colour too. We have also investigated the relationship between
electro-optical/chromogenic response and physical chemical properties of the components.
& 2008 Elsevier B.V. All rights reserved.

1. Introduction The physical principle used in all liquid crystal-based systems


is the electrically driven reorientation of liquid crystal directors,
Electrically switchable chromogenic materials (ESCMs) are which results a change in their transmittance values [9,10].
glazing devices that change either their colour or transmittance Among them polymer dispersed liquid crystals (PDCLs) are
upon application of a suitable electric eld. The most important composite materials, which show both the advantages of a solid
types of such devices are electrochromic windows, which change polymer and a uid liquid crystal. In fact, they are formed by
their colour, and dispersed liquid crystal and dispersed particles either micron-sized liquid crystal droplets embedded in a polymer
that allow controlling the scattering of the impinging light. ESCMs matrix, or by liquid crystal that lls the voids and crevices of a
can be used as smart windows for building and automotive polymer network. In the OFF state PDLCs appear translucent white
applications in order to control incident daylight and glare [13], due to the light scattering. Upon application of a suitable electric
according to occupant comfort. ESCMs are currently limited to eld, the molecular reorientation will change the refractive index
side and rear-view mirrors, sunglasses, sun-roofs and, in general, of liquid crystal domains and the device will appear transparent in
small area glazing. They are also expected to lower the demand on the ON state if the optical matching condition between the
precious non-renewable fuels for lighting and cooling. refractive indices of liquid crystal and polymer matrix is fullled.
Both inorganic- and organic-based electrochromic windows are Reverse mode operation PDLCs are devices which are transparent
the most popular ESCMs as conrmed by large number of scientic in the OFF state and turn opaque in the ON state. They allow
publications in recent years [48]. The major advantage of overcoming some drawbacks of direct mode PDLCs such as the
electrochromic materials is that the low electric eld must be opaque unpowered state and the large values of haze. Reverse
applied only during the switching operations. Organic electro- mode shutters have been obtained by using dual frequency
chromics are based on bipyridilium systems, conducting polymers, addressable liquid crystals [11,12], by polymerizing nematic
quinones, phthalocyanines, terephthalates, tetrathiafulvalenes, emulsions [13], and by functionalizing the liquid crystal/polymer
and cyanobiphenyls, which are molecules able to change their matrix interface [14]. Recently, we proposed a reverse mode
colour in response to oxidation/reduction processes. device obtained by the photopolymerization of mixtures contain-
ing a low-molecular-mass liquid crystal with a negative dielectric
anisotropy, and a liquid crystalline diacrylate monomer home-
otropically aligned by means of rough surfaces [15]. The align-
 Corresponding author. Tel.: +39 0984 493194; fax: +39 0984 493298. ment is achieved through typical grooves present in the
E-mail address: ore.nicoletta@unical.it (F.P. Nicoletta). substrates, which promote an excellent anchoring and an easy

0927-0248/$ - see front matter & 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.solmat.2008.11.010
ARTICLE IN PRESS

330 D. Cupelli et al. / Solar Energy Materials & Solar Cells 93 (2009) 329333

axis almost perpendicular to the cell glass plates. Such prefer- substrates [15]. After checking the homeotropic alignment of
ential alignment can be stored if crosslinkage of the polymerizable mixtures by polarizing optical microscope, cells were exposed at a
component is performed. controlled temperature (80 1C) to UV light for 15 min (average
The use of rough surfaces allows an easier and faster power 10 mW/cm2) in order to induce the phase separation
preparation since neither surface treatment of supports nor the between the liquid crystal and the polymer. The electro-optical
use of external aligning elds is required. In addition, no limit is properties of samples were measured with the optical setup
theoretically imposed on the dimensions of devices. previously reported [20] and the colour changes were monitored
More recently, we have shown that electrolyte/liquid crystal as a function of time and applied dc elds with a YASCO V550
dispersions are able to give both an independent and fast UVVis spectrometer. The intensity of the incident light measured
switching from a scattering opaque state to a transmissive through an empty cell was assumed to be full-scale intensity. The
transparent state, owing to liquid crystal director reorientation, ON and OFF response times, tON and tOFF, dened, respectively, as
and a colour change, due to the electrochromic reactions the time required to drop to 10% of the maximum transmittance and
occurring at the electrodes [16]. Both changes are obtained with to reach 90% of the optical response after the external eld is
rather fast switching and relaxation times: few milliseconds and removed, were determined by monitoring the drive signal (n 1
few seconds for the electro-optical and electrochromic responses, kHz, Epp 4 V mm1) and the response of the photodiode using a
respectively. The origin of electrochromism can be attributed to digital storage oscilloscope.
the formation of coloured complexes between phenyl rings and
ammonium ions, as reported by Nakamura et al. [17,18]. The
bleaching occurs when the dc eld is removed and is attributed to 3. Results and discussion
the diffusion of halide molecules produced by oxidation at the
anode and their reaction with coloured species. In this paper we 1,4-bis{4-[6-(acryloyloxy)hexyloxy]benzoyloxy} benzene is
will show our efforts devoted to the fabrication and characteriza- known to allow and keep after the polymerization, a good
tion of electrically switchable chromogenic cells suitable for homeotropic alignment of liquid crystal on rough substrates
external glazing obtained by doping with electrolytes reverse covered by indium tin oxide [15,21,22]. In fact, highly transparent
mode operation PDLCs. They are really bifunctional devices (OFF state transmittance, T, around 80%) and uncoloured PDLC
characterized by a transparent OFF state, which can become lms were obtained after the polymerization-induced phase
opaque upon application of an ac eld and can independently turn separation process. If an ac external eld is applied (n 1 kHz),
coloured, if a dc eld is applied. Such smart windows could be liquid crystal directors will reorient perpendicularly to the eld
used both for building and automotive applications allowing a direction because of its negative dielectric anisotropy, increasing
controlled comfort from daylight and glare. the light scattering and reducing the transmittance values (about
1% for an electric eld of 1.8 V mm1). Fig. 2 reports the typical
eld-dependent transmittance of a cell and shows that there is no
2. Experimental part

The nematic liquid crystal used in this work was the eutectic
mixture ZLI 4788-000 (Merck) characterized by a negative di-
electric anisotropy (De 5.7). Liquid crystalline monomer, 1,4-bis
{4-[6-(acryloyloxy)hexyloxy]benzoyloxy} benzene (Fig. 1), was
synthesized in agreement with literature [19]. 1% of ammonium
salts, tetrabutylammonium tetrauoroborate, tetrabutylammonium
hexauorophosphate, tetrabutylammonium perchlorate, octadecyl-
trimethylammonium bromide, and didodecyldimethylammonium
bromide (Aldrich) were dissolved in liquid crystal by stirring at
65 1C. The choice of ammonium salt can produce a change in the
intensity and shade of the cell colour [15]. Mixtures were prepared
in vials by mixing the appropriate amounts of liquid crystalline
monomer, 16 wt%, and ammonium salt-doped ZLI 4788-000,
84 wt%, and subsequently stirring them at 100 1C. Then, a small
quantity of mixtures was introduced by capillarity into home-made
cells whose thickness was set to 60 mm by glass spheres. Glass
substrates had a 120 nm indium tin oxide conductive layer (Balzers)
with an average roughness of 2.6 nm, which allows the alignment of
liquid crystalline mixtures perpendicular (homeotropic) to glass Fig. 2. Typical electric eld-dependent transmittance of our ESCM.

o
o o
o
o
o
o
o
o
o

Fig. 1. Molecular structure of used liquid crystalline monomer, 1,4-bis{4-[6-(acryloyloxy)hexyloxy] benzoyloxy} benzene.
ARTICLE IN PRESS

D. Cupelli et al. / Solar Energy Materials & Solar Cells 93 (2009) 329333 331

particular effect due to the presence of an electrolyte with respect


to a conventional reverse mode PDLC. It is possible to distinguish
three different regimes: (1) a lower electric eld range (Eo1.0 V
mm1) where the lms appear transparent, (2) a larger electric
eld range (E41.6 V mm1) in which the cells look opaque, and,
nally, (3) an intermediate range (1.0 V mm1oEo1.6 V mm1)
where one can tune the value of transmittance as a function of
impinging radiation intensity. The cell acts as an anti-dazzle
device, which dampens the intensity of the light so that the user is
never dazzled either by sunlight or by car lights during the night.
Scanning electron microscopy conrms the presence of poly-
mer ball morphology in all our samples: small polymer balls
(average radius about 100 nm) merging in a network structure,
whose voids and crevices are lled by liquid crystal (Fig. 3). Such a
structure allows a large angle view as thin liquid crystal layers
around the polymer droplets do not give rise to a sufcient phase
shift of the light [23]. As a result, the highly transparent state is a
consequence of both the polymer ball morphology of samples and
the good match between the polymer matrix refractive index and
liquid crystal ordinary one. If the external eld is removed, the
restoring forces acting at polymer and substrate interfaces will Fig. 4. Electro-optical response to an ac eld. Both ON and OFF response time
cause the homeotropic reorientation of directors (Fig. 4). Both tON values are of the order of few milliseconds.
and tOFF values are of the order of few milliseconds as in
conventional reverse mode PDLCs (tONE30 ms and tOFFE4 ms).
The increase of electrolyte concentration in samples causes a
decrease in the rise and decay times, due to a faster onset and
depletion of the local elds acting on droplets [15,24].
If a dc electric voltage of 2 V (or larger) is applied, the device
turns dark rose as conrmed by the appearance of an absorbance
peak in the green range of Vis spectrum. Fig. 5 is the difference
between the dc ON state and the dc OFF state in the cases of ac ON
and OFF. The resulting spectra are identical, showing the
independence of the effects. As a consequence, the application
of the dc eld could allow a better contrast for the vision of
objects against a green or blue background as purple and rose
lters offer.
The colouration and bleaching times, tcolour and tbleaching, i.e.
the times required to reach the fully coloured state and to come
back to the transparent state, are of the order of few minutes
(tcolourE2 min and tbleachingE0.5 min) as shown in Fig. 6. Follow-
ing the mechanism of colouration and bleaching proposed by
Nakamura et al. [17,18] for the electrochromism of liquid crystal
materials, the application of a dc current to our cells for a time Fig. 5. Chromogenic change upon application of a dc voltage (2 V). The device
equal to tcolour causes the migration of ammonium ions A+ to the looks dark rose.
cathode, where the reaction between A+ and ZLI liquid crystal,

A++ZLI+e-A*ZLI , takes place and gives a coloured complex. At


the same time halide molecules, Ha2, are produced at the anode.
These last molecules diffuse and react with the coloured species
according to the following reaction: 2A*ZLI+Ha2-2A++2
ZLI+2Ha, determining the bleaching of the sample when the dc
external eld is removed in tbleaching seconds. tcolour depends both
on electrolyte concentration and dc current application time
while tbleaching is only dependent on electrolyte concentration.
Short bleaching times can be obtained by shortening the cells.
The choice of halide counterions does not affect the colour of cells.
The combined electro-optical and electrochromic behaviours were
examined by spectroelectrochemistry by applying different
electric elds, as shown in Fig. 7. The four distinct states are

(1) transparent and uncoloured, when no eld is applied;


(2) transparent and coloured, if a dc electric eld is applied;
(3) opaque and uncoloured, when an ac electric eld is turned on;
and
Fig. 3. Scanning electron microscopy picture of sample morphology. The average (4) opaque and coloured, if both the ac and dc electric elds are
diameter of polymer ball is about100 nm. Scale bar is 200 nm. present.
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332 D. Cupelli et al. / Solar Energy Materials & Solar Cells 93 (2009) 329333

the control of incident daylight and glare in building and


automotive applications. The proposed device is able to change
its electro-optical transmittance within few milliseconds and its
colour within few seconds. The application of an ac eld allows to
dampen the intensity of the light while the addition of a dc eld
allows to gain a better contrast.
The lms represent a further development of bifunctional
devices, which do not need the use of any particular chemical,
such as conductive oligomers, and of other electrochromic
molecules, such as viologens. The matrix conductivity is oppor-
tunely increased by the electrolyte solution and the liquid crystal
acts as a chromogenic molecule. In addition they grant transpar-
ent OFF states and opaque ON states. These lms can be
considered solid electrochromic lms self-supporting and can be
subsequently laminated between conductive substrates. Their
self-supporting nature provides many benets to the electro-
chromic devices manufactured within, including the enhance-
ment of processing and, from a safety perspective, in the event
that electrochromic devices should break or become damaged, the
polymer matrix is able to impede seepage of uid components in
the environment.

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