Chapter 1

Chromogenic Effects in Polymers: An Overview

of the Diverse Ways of Tuning Optical Properties
in Real Time
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1 2
Samson A . Jenekhe and Douglas J . Kiserow
Downloaded via 201.48.108.173 on January 11, 2022 at 11:33:21 (UTC).

1
Department of Chemical Engineering, University of Washington,
Seattle, WA 89195-1750
2
Polymer Chemistry Branch, U.S. Army Research Office, P.O. Box 12211,
Research Triangle Park, NC 27709-2211

In this overview chapter we introduce the subject of

chromogenic phenomena in polymers and briefly review some
of the recent advances in the field. Many external stimuli-
-responsive phenomena in polymers, including
electrochromism, photochromism, photoelectrochromism, and
piezochromism are discussed. Relatively new approaches to
dynamic tunability of optical properties, such as
mechanochromism, tunable electroluminescence and photonic
band gap structures in polymers, are also discussed. There are
good prospects that future advances in chromogenic polymers,
particularly the integration of multiple chromogenic effects in
the same material system, will usher in an era of "intelligent"
materials for many technological applications.

2 © 2005 American Chemical Society

Jenekhe and Kiserow; Chromogenic Phenomena in Polymers

ACS Symposium Series; American Chemical Society: Washington, DC, 2004.
 3

The reversible change of the optical properties of a material, such as color,

absorption spectrum, emission spectrum, or refractive index, by means of an
external stimulus represents an example of a chromogenic phenomenon. Many
chromogenic phenomena have been extensively documented and widely
investigated in organic materials and polymers in the past three decades (1-18).
The chromogenic effects associated with reversible color changes induced by
applied electric, optical, thermal, pressure and magnetic fields are respectively
known as electrochromism, photochromism, thermochromism, piezochromism
and magnetochromism (1-8). The materials involved are said to be
electrochromic, photochromic, thermochromic, piezochromic and
magnetochromic, respectively. In addition to these, other chromogenic

TUNABLE
ELECTROLUMINESCENCE

ELECTROCHROMISM

PHOTONIC BAND GAP

PIEZOCHROMISM
(PBG)

THERMOCHROMISM SELECTIVE
REFLECTION

PHOTOCHROMISM MECHANOCHROMISM

PHOTOELECTROCHROMISM

Figure 1. Main examples of chromogenic phenomena observed in

organic polymers.

phenomena of growing interest in polymers are included in Figure 1. Different

aspects of chromogenic phenomena in materials, including organic materials,
have been covered in prior reviews and books (1-12). Here we focus mainly on
chromogenic effects in polymeric materials.
It is useful to distinguish between dynamic or real time tunability of optical
properties and static tunability. Nearly all of the different materials associated
with the chromogenic phenomena cited in Figure 1 are such that the applied
external stimulus in principle provides a ready means to reversibly tune or
control their optical properties in real time. The optical properties of a polymeric
material can also be changed in a static or trivial fashion, for example through
change of the molecular structure or composition by synthesis or the solvent
medium. The phenomenon involved in the change of the color of a polymer in
solution when the solvent is changed is called solvatochromism and the material

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ACS Symposium Series; American Chemical Society: Washington, DC, 2004.
4
is said to be solvatochromic (72). This latter effect is an example of static
tunability which will not be discussed further.
Only several of the chromogenic phenomena cited in Figure 1 will be briefly
discussed below because of space limitation. Recent advances in nearly all of
these areas can be found in the following chapters of this book.
Thermochromism, for example, occurs widely in many π- and σ-conjugated
polymers and thermochromic polymers are discussed in some prior reviews (7-3,
8). We conclude from our review of the literature that the development of
chameleon-like "intelligent" materials is feasible and can be facilitated by further
advances in multifunctional chromogenic polymers.

Photochromic Polymers

A molecule that undergoes a reversible photoinduced change between two

states with different optical properties such as color or absorption spectrum is
considered to be photochromic. The chromogenic effect, photochromism, can be
illustrated by the photochemical transformation of molecule A to Β upon
absorption of light:

hv (or Δ)
2

The back reaction can occur photochemically with absorption of longer

wavelength or thermally. Normally, species A has an absorption spectrum that is
blue shifted from that of species B. Besides the reversible changes in the
absorption spectrum, and hence color, the emission spectrum, refractive index,
dielectric constant and other physicochemical properties of a photochromic
material may also be tuned or controlled by light (7-5).
Numerous photochromic organic molecules are known and have been
extensively investigated in solution, as solids and most importantly in polymers.
Important examples of photochromic molecules include aromatic azo
compounds, spirobenzopyran and derivatives, spirooxazines, fulgides,
fiilgimides and diarylethenes (2-5). The synthesis and photochromic properties
of these and other classes of photochromic compounds are described in many
reviews and books (7-5). It is the incorporation of these diverse photochromic
molecules into polymers, either through physical blending or covalently, that has
substantially advanced their technological applications in many areas. One oi e
well known commercial applications of photochromic polymers is in plastic
lenses of variable optical density; the self-adjusting lenses darken under sunlight
and become relatively clear inside (5-5). Among the many other applications that
exploit the photochromic properties of polymers include optical filters for
12 3
cameras, ultrahigh density (~10 bits/cm ) 3D optical memories (2b, 13), real

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time holography, fluid flow visualization, displays and security printing inks (3-
5,9-11,13).
6
Achieving high photochemical cycling rates (>10 cycles) without fatigue
remains one of the major challenges in using photochromic polymers for high
performance applications such as optical memories and displays. Detailed
studies of the dynamics of the photocoloration and the reverse photo- or thermal-
bleaching processes of the most promising photochromic polymers are of
interest. Development of new photochromic polymer systems with substantially
improved fatigue resistance is essential to success in currently known
applications of the materials. Another area of future direction of research is the
coupling of photochromism with other chromogenic effects or important
physical property in the same material. Photoelectrochromism which facilitates
the optical control of electrochromism is an early example of this (6,14a).
Photomagnetism wherein the magnetic properties of a material are controlled by
light absorption is another (14b, 14c).

Electrochromic Polymers and Devices

An electrochromic (EC) material undergoes a reversible change in color or

other optical property under an applied electrochemical potential (6). An EC
material is also referred to as an electrochrome. The underlying phenomenon,
electrochromism, arises from the different electronic structures and thus optical
properties of an EC material in the different redox states accessible by switching
the applied voltage. An electrochrome that changes color upon oxidation is an
anodic EC material. Similarly, a cathodic EC material is one that changes color
upon reduction. Although other classes of EC materials are known, including
inorganic metal oxides (WO ,Ti0 ) and organic small molecules (1,2,6), we
x 2

focus here on conducting polymer-based EC materials and electrochromic

devices (ECDs) made from them. Applications of such electrochromic devices
include large area displays, variable transmittance ("smart") windows and
variable reflectance mirrors.
π-Conjugated polymers are well suited to be EC materials because their
oxidation or reduction is accompanied by substantial changes in optical
absorption spectra in the visible and near infrared regions. Indeed, there is a vast
literature on conducting polymer-based EC materials and devices (6,7,15-18). In
their neutral forms conjugated polymers have optical band gaps (Eg), arising
from π-π* optical transitions, in the visible to near infrared range (-1-3 eV).
New optical transitions due to the formation of polaron and bipolaron charged
states are observed on oxidation or reduction of the materials. Since the optical
spectra of a conjugated polymer vary continuously with the degree of oxidation
or reduction, multiple colors are possible and are commonly observed with
conducting polymer ECDs.

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Typical conjugated polymers that have been explored as EC materials are
shown in Figure 2. Polythiophenes (1), polypyrroles (2), polyaniline (3),
poly(3,4-ethylenedioxythiophene) (4) and related derivative (5) are examples of
anodically coloring electrochromic materials (6,7,15-18). Ladder
poly(benzimidazolebenzophenanthroline) (6, BBL) and polyphenylquinoline (7)
are examples of cathodically coloring EC materials (18b, 19).

ι
Figure 2. Examples of conjugated polymer EC materials.

Tunable Emission and Electroluminescence

Many conjugated polymers in solution or as thin films show strong

photoluminescence (PL) under photoexcitation. Examples of some
photoluminescent conjugated polymers are shown in Figure 3. Poly(p-
phenylenevinylene) (PPV) thin films emit green light whereas its derivative,
poly(2-methoxy-5-(2 '-ethy lhexyloxy)-1,4-phenylenevinylene) (MEH-PPV),
exhibits orange-red photoluminescence as are poly(4-phenylquinoline) (PPQ)
thin films. In contrast, poly(9,9'-dioctylfluorene) (PFO) thin films emit blue
light. By sandwiching a PPV thin film between a transparent indium tin oxide
(ITO) conductor and aluminum and applying a voltage, as shown in Figure 3,
electroluminescence (EL) from conjugated polymers was discovered in 1990
(20). The resulting EL emission spectrum of PPV was identical to the PL
emission spectrum. A few years earlier, similar thin film light emitting diodes
(LEDs) were demonstrated with a small molecule organometallic compound
(aluminum quinolate, Alq ) (21). Hundreds of organic molecules and polymers
3

have since been found to be similarly useful as emissive materials for LEDs (20-
24). Substantial progress has been made in developing organic and polymer
LEDs of various colors for flat panel displays (20-24).

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MEH-PPV ppQ
Figure 3. Examples of electroluminescent polymers and schematic of a simple
polymer light emitting diode.

An organic or polymer LED (Figure 3) normally emits one color at all

applied voltages. The color of light emitted from such a diode is determined by
the electronic structure of the emissive polymer layer. However, if the LED is
constructed from a multicomponent polymer system with two or more emissive
components, voltage-tunable multicolor emission can result from the LED
(23,24). Tunable multicolor EL has thus been achieved in LEDs fabricated from
nanophase-separated blends (24), bilayer thin films (23), multilayer thin films
(23), and nanophase-separated block copolymers. In such LEDs a different EL
spectrum, and thus color, can be obtained at different applied voltages as
illustrated in Figure 4. For example, a bilayer LED constructed from a green-
emitting PPV layer and an orange/red-emitting PPQ layer, ITO/PPV/PPQ/A1,
exhibited many different colors under applied bias voltages of 6-13V as shown
in Plate 1 (23b).

Wavelength

Figure 4. Schematic of a voltage-tunable multicolor polymer

LED and the resulting EL emission spectra.

The voltage-tunable multicolor EL emission from bilayer polymer LEDs,

such as in Plate 1, arises from variation in the EL emission intensity coming
from the different layers and a physical mixing of the EL emission from both
polymers. A similar mechanism explains the multicolor EL emission from
nanophase-separated blends (24) and other multicomponent EL polymer systems

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ACS Symposium Series; American Chemical Society: Washington, DC, 2004.
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Jenekhe and Kiserow; Chromogenic Phenomena in Polymers

Plate L Multicolor emissionfromITO/PPV(35 nm)/PPQ(35 nm)/AI diodes at
various bias voltages (from ref. 23b). (See page 1 of color insert)

ACS Symposium Series; American Chemical Society: Washington, DC, 2004.

 9

(23). The relative film thicknesses of bilayers and multilayers, and domain sizes
in the case of blends, play a critical role in the ability to achieve multicolor
emission from LEDs based on multicomponent emissive materials. The reason
for this is due to the electricfield-dependenceof the charge carrier mobilities in
the materials (23). The interchromophore photophysics also places a bound on
achievable multicolor emission in such multichromophoric systems (25). In
particular, energy transfer, exciplex formation, and photoinduced electron
transfer among the different components must be minimized in order to obtain
multicolor emission from the different components (23-25). Blends of
polyfluorene (PFO) and MEH-PPV, for example, show one-color (orange) EL
because of the very efficient energy transfer from the blue-emitting PFO to the
smaller energy gap MEH-PPV.
Voltage-tunable multicolor EL emission from polymer systems, which is
briefly described here, represents a novel chromogenic effect that has emerged
from recent studies of emissive polymer semiconductors. There is no analogous
effect in inorganic semiconductors. Besides flat-panel displays, other
applications includingflexibledisplays, traffic lights, and biological imaging can
be envisioned for real time tunable multicolor polymer LEDs.

Mechanochromic Polymers

Color change induced by applied mechanical stress in a material is termed

mechanochromism. Such mechanically-induced color changes have been
observed infree-standingand substrate-supported polydiacetylene (PDA) films
(26,27). Both tensile stress and shear stress can effect chromic transitions in
PDA films. Examples of polymers or polymer segments that facilitate
mechanochromism are shown in Figure 5. Elastomeric segmented poly(urethane-
co-diacetylene) copolymer films were shown to undergo reversible color changes

Figure 5. Examples of mechanochromic polymers.

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when stretched to strains of 250-300%. The blue unstretched elastomer film

changed to red or yellow depending on the degree of strain. The resulting red or
yellow film returned to its original blue color when the tensile strain was
removed. Visible absorption spectroscopy showed that the stress-induced color
changes are due to order-disorder transitions of the conjugated PDA chains
within domains of the hard segments of the polyurethane elastomer.
Recent work has extended mechanochromism in the polydiacetylenes to the
nanoscale. Studies of Langmuir-Blodgett films of PDAs on mica or silicon oxide
substrates have shown that the tip of an atomic force microscope (AFM) can be
used to induce local changes in color, demonstrating nanometer scale
mechanochromism. The blue-to-red change in color of PDA monolayers was
caused by the shear stress on the film due to tip/film contact and friction. This
chromic transition is related to the mechanochromism observed in the bulk films
(26) as well as previous observations of solvatochromism and thermochromism
in many different polydiacetylenes (28). The nanoscale color changes were
irreversible. Potential uses of this nanoscale mechanochromism include optical
sensor/detection of contact, friction, and adhesion if the mechano-optical effect
can be made reversible through improved materials.
A thermoplastic polyurethane elastomer that undergoes irreversible change
in optical absorption with tensile strain has been demonstrated as a strain-
recording "smart" material (29). An azobenzene chromophore that undergoes
cis-trans isomerization was covalently embedded in the polyamide segment of
the elastomer. Deformation due to applied tensile stress converts the azobenzene
chromophore to the trans form and consequently an increase in the long
wavelength absorption. Irreversibility allows retention of information about the
strain. Intended applications of such an irreversible mechanochromic polymer
include components of smartfiber-reinforcedpolymer composites that are able
to respond to a changing environment and send out warning signals prior to
structural failure (29). Obvious potential systems applications include smart
skins on bridges or aircraft wings and panels (29).

Piezochromic Polymers

The change of optical properties with pressure is known as piezochromism

(1,30-38). The change of color by a solid under compression at high pressures
exemplifies this chromogenic effect. Because significant changes in optical
properties occur only at relatively high pressures, the possible application of
piezochromic materials is unclear. Unlike many other classes of chromogenic
materials, studies of piezochromism in conjugated molecules and polymers are
thus largely motivated by interest in gaining fundamental information about how
interchain interactions influence the electronic structure and optical properties of
the materials.

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Two underlying mechanisms of color change in a piezochromic material

have been advanced (/). In a polymorphic crystalline solid that has one phase at
ambient pressure and another at high pressure, the corresponding colors or
optical properties of the two phases can be observed by pressure-induced phase
transition. Alternatively, pressure-induced changes in molecular geometry and
intermolecular interactions of the molecular solid can facilitate the continuous
variation of optical properties with pressure. The latter mechanism appears to

trans-FA PPP P3AT

PAQ R= C H 1 6 3 3

Figure 6. Examples of polymers exhibiting piezochromism.

account for the observed piezochromism in many σ - and π-conjugated polymers

that have been reported (30-38).
Examples of polymers known to exhibit piezochromism are shown in Figure
6. Studies of the optical absorption spectra of undoped ir<ms-polyacetylene
(trans-ΡΑ) under pressure from ambient to about 5 GPa at 300K showed that it
exhibited reversible piezochromism (30). The optical absorption edge band gap
(E ) decreased from 1.4 eV at ambient pressure to 0.85 eV at 5 GPa. However,
g

pressure-induced reactions occurred in the 5-8 GPa range, leading to an

apparently cross-linked material that was transparent to visible light above this
range of pressures. In contrast, crystalline samples (30 μηι initial thickness) of
poly(p-phenylene) (PPP) were found to be robust with no reaction at pressures as
high as 20 GPa (31). The measured optical absorption spectra of PPP films
under pressure from ambient to 20 GPa revealed reversible piezochromism. The
optical band gap E decreased monotonically from 2.74 eV at ambient to 2.19
g

eV at 20 GPa. This represents a 0.55 eV reduction in E value at 20 GPa

g

compared to ambient. This pressure-induced red shift in the absorption spectrum

of PPP was explained by the increase in interchain interactions and decrease in
the torsion angle between rings (31).
Reversible piezochromism has been observed in regioregular and
regiorandom poly(3-alkylthiophene)s (32-35). Optical absorption spectra of
solutions of poly(3-hexylthiophene) (P3HT) in toluene were observed to exhibit
large bathochromic shifts with increasing hydrostatic pressure, compared to
ambient pressure. The optical band gap of P3HT in toluene solution was 2.4 eV
under ambient pressure but was reduced to 1.7 eV at 8 kbar (0.8 GPa) (32).

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Similar results were obtained for other poly(3-alkylthiophene)s with alkyl chain
lengths exceeding butyl. These piezochromic properties of poly(3-
alkylthiophene)s were explained by pressure-induced change of the polymer
conformation and particularly the reduced torsion angle between rings at high
pressure (32). In accord with the observations in solution, the optical
absorption and photoluminescence (PL) spectra of P3HT films showed
reversible piezochromism up to 0.8 GPa (33). Essentially similar results and
conclusions were reached for regioregular and regiorandom poly(3-
octylthiophene) (35). Interestingly, the observed thermochromism of P3HT
under ambient was completely suppressed at 1.4 GPa (33). Studies of the
piezochromic properties of P3HT to much higher pressures revealed new effects,
including hysteresis in the absorption spectra and dc conductivity data under
compression and decompression (34). The absorption maximum energy and
optical band gap decreased to a minimum at about 3 GPa and were followed by
an increase with further increase in pressure. The dc conductivity of the undoped
P3HT films under pressures of up to 5 GPa had a maximum at about 2 GPa,
followed by a large decrease. The observed increase in optical band gap or blue
shift in the absorption spectrum after the 3 GPa minimum was explained by
P3HT backbone bending at the very high pressures (34).
Conjugated poly(5,8-dihexadecyloxyanthraquinone-l,4-diyl) (PAQ) films
were observed to exhibit reversible piezochromism up to 11 GPa. The orange-
yellow films at ambient pressure progressively change to dark red at 11 GPa
(36). The associated optical band gap decreased from 2.42 eV (ambient) to 1.5
eV at 11 GPa. The observed piezochromism was interpreted as due to pressure-
induced shortening of the π-π interchain distance. Interestingly, piezochromism
was not observed in the homologous polyanthraquinones with shorter dialkoxy
side chains. Polydiacetylenes (PDAs) with various side groups have reported
piezochromism in solution, as gels and as films (37). For example, a yellow
solution of poly(nBCMU) at ambient pressure turns red at high pressures (1.6-
3.8 GPa) (37). Piezochromism has also been observed in various σ-conjugated
poly(di-n-alkylsilane)s (PDASi) (38). Both cases of pressure-,induced red shift
and blue shift have been observed for different polysilanes (38). These
piezochromic properties have also been understood in terms of pressure-induced
changes in the conformation of the polysilanes. In general, it is very likely that
most conjugated polymers, particularly those bearing side chains, will show
piezochromic properties at sufficiently high pressures. An important question for
workers in this area is: can applications be found for this interesting
chromogenic phenomenon?

Polymer-Based Photonic Band Gap Composites

The development of materials or structures that possess a photonic band gap

(PBG) and the development of devices exploiting this effect are currently of

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intense and wide interest (39-44). A PBG material or photonic crystal is an

artificial dielectric composite that has a periodic modulation of the refractive
index on a distance scale of half an optical wavelength (39). Consequently, a
photonic crystal hasfrequencybands for which light cannot propagate but can be
confined. A quarter-wave-stack optical interference filter is a simple one-
dimensional (1-D) example of a photonic crystal. Interest in two-dimensional (2-
D) and three-dimensional (3-D) PBG materials stems from the dramatic
modification of the propagation properties of light within such a material. Many
novel optical properties, including complete confinement of light of certain
frequencies, substantial modulation of the refractive index, modulation of
spontaneous emission and tunable reflectivity, are predicted for 3-D PBG
materials. Applications ranging from zero-threshold lasers, sensors, optical
communication and optical switching devices to ultrahigh density 3-D optical
memories are envisioned (39-44). 3-D photonic crystals, with photonic band
gaps in the visible to near infrared spectral range, have been madefroma variety
of polymer composites (40-44). These include polymer-air composites created
from opals, inverse opals and block copolymers, polymerized crystalline
colloidal arrays, homopolymer/block copolymer blends and two-photon
photopolymerized structures (40-44).

Acknowledgments

We acknowledge the support by the U . S. Army Research Office TOPS

MURI Program (Grant no. DAAD19-01-1-0676), the NSF STC (Grant no.
DMR-0120967) and the Boeing-Martin Professorship Endowment.

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Jenekhe and Kiserow; Chromogenic Phenomena in Polymers

ACS Symposium Series; American Chemical Society: Washington, DC, 2004.