Indigo and Tyrian Purple

Review
DOI: 10.1002/ijch.201100130
Indigo and Tyrian Purple From Ancient Natural Dyes to

Modern Organic Semiconductors
Eric Daniel Gowacki,*[a] Gundula Voss,[b] Lucia Leonat,[c] Mihai Irimia-Vladu,*[a, d] Siegfried Bauer,[d] and
Niyazi Serdar Sariciftci[a]
Dedicated to Prof. Ching W. Tang, our friend and mentor
Abstract: We describe the history of indigo dye and its derivative Tyrian purple, from their roles in the ancient world to
recent research showing the semiconducting properties of
indigoids. Indigoids are natural dyes that have been produced for centuries, and indigo is currently the most produced dye worldwide. Herein we review the history of these
materials, their chemistry and physical properties, and their
semiconducting characteristics in the solid state. Due to hydrogen bonding and p-stacking, indigo and Tyrian purple
form highly-ordered crystalline thin films. Such films have

been used to fabricate high-performance organic field-effect
transistors with ambipolar charge transport, as well as complementary-like circuits. Mobility values were found to be in
the range of 1020.4 cm2/Vs. With performance on par with
the best available organic semiconductors, indigoids demonstrate the potential of sustainable electronics based on
biodegradable and biocompatible materials.
Keywords: organic electronics organic field-effect transistors natural products biocompatible materials hydrogen bonding
1 Introduction
The world around us is in colour. Humans have used dyes
for thousands of years (since before 10,000 BC). The
oldest examples are prehistoric cave paintings, which
show the already-sophisticated use of carefully-graded
colours. What is striking is the lack of blue pigments.
Indeed, blue dyes are rare in nature, which is perhaps the
reason for associating blue and purple shades with
wealth. From the cloth wrapping of mummies and the ancient Israelite sacred pigment Tekhelet to the colours of
the uniforms of Napoleons soldiers and modern jeans,
indigo and Tyrian purple are among the most historic
structures in organic chemistry (Figure 1).[13] In our
recent work, we have focused on natural and nature-inspired materials for organic electronics applications.[46]
Organic electronics are proposed for applications ranging
from smart RF-ID packaging tags to electronics embedded in textiles, for instance. This emerging field is motivated by the idea of mass-producing cheap and sustainable electronic devices for display applications, photovoltaic cells, and integrated-circuits and sensors. Future largescale application of sustainable organic electronics based
on biodegradable materials would have a positive impact
on the current problem of electronic waste. Our attention
to historic dyes has been inspired by the idea of tapping
into this massive and highly-developed body of chemical
and chemical engineering knowledge to find materials
that are potentially useful in electronics.
This review is divided into four sections: The first describes the history of indigoids. The second covers the
Isr. J. Chem. 2012, 52, 1 12
chemistry of these dyes, from elucidation of the chemical

methods used in the ancient world to modern synthetic
routes. The third section discusses the chemical physics of
indigo, including the photophysics and the influence of
hydrogen bonding. The fourth describes the recent discovery of promising semiconducting properties in indigo
and Tyrian purple.
2 The History of Indigoids
Indigo and Tyrian purple (main constituent 6,6-dibromoindigo) have been known for at least 4000 years. Their
structures are shown in Figure 1, with the production
[a] E. D. Gowacki, M. Irimia-Vladu, N. S. Sariciftci
Linz Institute for Organic Solar Cells (LIOS)
Johannes Kepler University, Linz (Austria)
e-mail: eric_daniel.glowacki@jku.at
mihai.irimia-vladu@jku.at
[b] G. Voss
Department of Bioorganic Chemistry
Bayreuth University, Bayreuth (Germany)
[c] L. Leonat
Faculty of Applied Chemistry and Materials Science
Politehnica University of Bucharest, Bucharest (Romania);
National Institute for Electrical Engineering, IPCE-CA, Bucharest
(Romania)
[d] M. Irimia-Vladu, S. Bauer
Department of Soft Matter Physics
Johannes Kepler University, Linz (Austria)
2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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These are not the final page numbers!
Review
E. D. Gowacki, M. Irimia-Vladu, et al.
Eric D. Gowacki completed his Bachelor (2009) and Master (2010) degrees
in chemistry at the University of Rochester, in Rochester, New York, USA
in the group of Prof. Ching Tang. The
subject of his MSc. thesis was doping
and degradation mechanisms of organic semiconductors. During the years
20072010, he was employed at the
Laboratory for Laser Energetics (LLE)
in Rochester, where he worked on photoactive liquid crystalline materials.
Since July 2010 he has been a doctoral
student in the Linz Institute for Organic Solar Cells (LIOS), under
the supervision of Prof. Niyazi Serdar Sariciftci. He has been engaged in projects studying indigoids and other hydrogen-bonded semiconductors, as well as spectroscopy of organic materials.
Mihai Irimia-Vladu was born in Craiova, Romania. He obtained his B.S in

Automotive Engineering from the University of Craiova and then worked as
an engineer at Daewoo Automobiles.
He completed his Ph.D. under the
guidance of Prof. Jeff Fergus in the Materials Engineering department at
Auburn University in Alabama, USA in
2006 in the field of conducting polymer-based sensors. He moved to Johannes Kepler University in Linz, Austria, to work in close collaboration with
the groups of Profs. Siegfried Bauer and Serdar Sariciftci. In Linz,
he is the initiator and principal investigator of implementing
green materials for organic electronics.
Gundula Voss was born in 1947 near

Rostock in the then German Democratic Republic - where she also studied
chemistry. She obtained a Ph.D. in
1978 from the University of Hamburg
on heterocyclic chemistry. After graduation she worked as research associate
at the universities in Aachen and Bayreuth where she received a permanent
position at the Department of Organic
Chemistry (now Bioorganic Chemistry).
Her present research focuses on the
structure-function relationship of indigoids in organic electronics. She is currently a visiting scientist at
the Linz Institute for Organic Solar Cells (LIOS).
Siegfried Bauer received his Ph.D.

degree in physics from the Technical
University in Karlsruhe in 1990. In 1992
he joined the Heinrich Hertz Institute
for Communication Engineering in
Berlin, Germany. In 1996 he earned his
Habilitation from the University of
Potsdam. In 1997 he became a Professor of Experimental Physics at the Johannes Kepler University in Linz, Austria. Since 2002 he has been head of
the Soft Matter Physics Department.
Dr. Bauers research is devoted to functional soft matter and its application in sustainable electronics and
energy harvesting. In 2012 Dr. Bauer was awarded with an European
Research Council Advanced Investigators Grant.
Lucia N. Leonat is a junior researcher

at The National Institute for Electrical
Engineering (ICPE-CA), Bucharest, Romania, having as her area of interest
surface characterization of materials by
methods of AFM, SEM and gas sorption analysis. She graduated with
a Bachelor in Medical Physics at the
Faculty of Physics, University of Bucharest. In 2009 she started her Ph.D.
study at the Politehnica University of
Bucharest, Faculty of Industrial
Chemistry and Materials Engineering.
During her Ph.D. study, she travelled to the Linz Institute for Organic Solar Cells to work under the guidance of Prof. Niyazi Serdar Sariciftci, in the area of nature-inspired organic materials for electronics.
Niyazi Serdar Sariciftci is Ordinarius

Professor for Physical Chemistry and
the founding director of the Linz Institute for Organic Solar Cells (LIOS) at
the Johannes Kepler University of Linz,
Austria. He studied at the University of
Vienna and graduated as a Ph.D. in
physics in 1989. After two years postdoctoral study at the University of
Stuttgart, he joined the Institute for
Polymers and Organic Solids at the
University of California, Santa Barbara,
USA, led by Prof. Alan J. Heeger, Nobel
laureate 2000 for Chemistry. His major contributions are in the
fields of photoinduced optical, magnetic resonance and transport
phenomena in semiconducting and metallic polymers. He is the inventor of conjugated polymer and fullerene solar cells. Prof. Sariciftci has published over 500 publications and with over 23,000 citations he is one of the most cited scientists in material science. He
has composed 8 books and educated several academic and industrial scientists. He has also initiated seven spin off companies for
organic optoelectronics.
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www.ijc.wiley-vch.de
Isr. J. Chem. 2012, 52, 1 12
Indigo and Tyrian Purple
Figure 1. The molecular structure of indigo (1) and Tyrian purple (2). The numbering scheme shown here is used throughout this paper
and in most literature on indigoids from the past sixty years.
steps from their bio-precursors in Scheme 1. Tyrian

purple was also known in literature as imperial purple or
antique purple, and in the ancient world was associated
with power and high status. In what might be considered
the worlds first chemical industry, indigoid dyes were
produced by processing organic precursors from plant or
animal sources (Scheme 1). These would be exposed to
reaction conditions to yield the final indigoid dye. This
ancient process also inspired the first modern chemical industry: the synthetic production of indigo in the late 19th
century became, for example, the source of wealth for
many German chemical companies.[13,7,8]
2.1 Indigo
Archaeological excavations show the use of indigo on the

Indian subcontinent for over 4000 years. It is most likely
that indigo plant cultivation spread from India, where the
dye precursors were extracted from species of the tropical
Indigofera plant. In medieval Europe, the indigo dye was
produced from the woad plant (Isatis tinctoria). The Thuringia region of Germany, and in particular the city of
Erfurt, became the centre of woad production in Europe.
The importance and wealth that indigo created for this
city is reflected by the foundation of one of the oldest

European universities there in 1392. Woad-derived indigo
is today most recognizable in medieval tapestries. In the
17th century import of higher-quality indigo from India
destroyed the European woad industry. Indian production
of indigo was dominated by the British during this time.
During the Napoleonic wars, the French-British naval
conflict and British blockade of continental ports resulted
in a resurgence of woad-derived indigo production, particularly with Napoleons choice of the indigo dye as the
colour of the uniforms of his Grande Arme soldiers. The
death-blow to the natural-origin indigo industry started
with Adolf von Baeyers discovery in 1883 of the chemical structure of indigo and his commercialisation of synthetic methods (Scheme 2) for producing indigo. These
early methods were not initially competitive with natural
indigo. It was not until 1897, after 1 million of research
investment from BASF that a practical synthetic route
was developed by K. Heumann, which was later improved
by J. Pfleger (see Section 3.2). Synthetically-produced
indigo was of superior quality to indigo from plants, and
was therefore preferred by dyers. Today indigo is the
most-produced dye in the world, with a worldwide pro-
Scheme 1. (a) Natural synthetic route to indigo from Indican in Indigofera tinctoria. (b) Tyrian purple (6,6-dibromoindigo) from tyrindoxyl
sulfate precursor, which is found in molluscs of the genus Murex.
Isr. J. Chem. 2012, 52, 1 12
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Review
Scheme 2. Representative syntheses of indigo.
duction of thousands of tons, most of which is used for

dyeing blue jeans. [13,78]
2.2 Tyrian Purple
Around 1500 BC, the ancient Phoenicians discovered that

certain Mediterranean sea snails produce secretions
which can stain textiles a deep violet colour. The extraction and dyeing process was extremely tedious, with thousands of snails being necessary to produce enough dye to
colour a single piece of cloth. Because of this, it was
worth its weight in gold. The Mediterranean city of Tyre
became the centre of this dyeing industry. In ancient
Israel, it was used by Israelite high priests and known as
Tekhelet, albeit in its blue form. Because of its colour and
rarity, the dye rose to prominence in the ancient world as
a symbol of wealth and power. For example, the dye
became the symbol of authority in Rome, where a stripe
of purple on the toga was a distinction worn only by senators. In the time of Gaius Julius Caesar strict rules existed
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to dictate who was permitted to wear Tyrian purple. The

expression in many languages of born into purple as indicating a privileged background originates from the
renown of Tyrian purple. It was recognised in the early
19th century that Tyrian purple was chemically-related to
indigo but it was not until 1909 that German chemist
Paul Friedlnder finally determined the structure to be
6,6-dibromoindigo after obtaining 1.4 g of Tyrian purple
from 12,000 snails. The dye, however, has never been produced industrially in the modern age.[2,3,712]
3 The Chemistry of Indigoids

3.1 Chemistry of Natural-Origin Indigoids
Although indigo and Tyrian purple themselves are not

present in nature, their immediate natural precursors are.
For indigo, direct precursors are of plant origin, such as
species of the Indigofera genus in the tropics (e.g. Indigofera tinctora, Indigofera fabaceae) and the woad plant in
Isr. J. Chem. 2012, 52, 1 12
Europe (Isatis tinctoria). In plants the precursor molecule

is indoxyl, which in the case of Indigofera tinctoria is attached to a glucose ring, forming the glucoside indican
(Scheme 1 a). After enzymatic cleavage of the sugar residue, the unstable indoxyl dimerises and then oxidises in
the presence of atmospheric oxygen to form stable indigo.
Tyrian purple, in contrast, is of animal origin. The precursor of the dye, tyrindoxyl sulfate (Scheme 1 b) is formed
in the hypobranchial glands of molluscs from the genus
Murex. These are marine shellfish living throughout the
Mediterranean. The formation of the indigoid dye involves the evolution of volatile sulfur compounds such as
disulfides and mercaptans, resulting in highly unpleasant
odours that led the authorities in ancient Tyre to banish
dyers beyond city limits. Contrary to many natural-origin
dyes, indigoids are extremely stable with respect to degradation, resulting in their persistent use throughout the
centuries.
3.2 Synthetic Routes to Indigoids
Indigo is currently the most-produced dye in the world.

In the early 19th century, it was already known that distillation of indigo yielded aniline. In 1869, Baeyer obtained
indole from the reduction of indigo. This and other available information led him to correctly propose the chemical constitution of indigo in 1883 (he proposed the cis
structure, it was later found that indigo exists in the trans
form due to hydrogen bonding). Prior to establishing the
structure, he succeeded in developing two synthetic
routes for indigo (Scheme 2: Baeyer, 1878; Baeyer, 1882).
The latter became the first commercialised synthesis,
starting from o-nitrocinnamic acid. This however proved
to be a poor competitor economically, as the multistep reaction produced indigo in only low yield. The Heumann
synthesis of indigo from 1897 and the 1901 Pfleger modification thereof proved most successful economically. The
most common synthetic routes to indigo are shown in
Scheme 2. Tyrian purple can be produced utilising the
Baeyer-Drewsen synthesis from 2-nitro-4-bromobenzaldehyde. Indeed, it was via this method that Friedlnder synthesised Tyrian purple for the first time. Indigo may also
be directly brominated to give 5,5- and 5,5,7,7-bromoindigos (as mixtures), but not 6,6-dibromoindigo, thus
many other synthetic routes to Tyrian purple have been

proposed.[13,8]
Introduction of substituent groups on the phenyl rings
of indigo precursors (i.e. anthralic acid, o-nitrobenzaldehyde) can be used to produce symmetrically-substituted
indigos. It is also possible to prepare asymmetrically-substituted indigoids via condensation of 2-chloroindolone
with indoxyl (Scheme 3). This method can be used, for instance, to prepare monobrominated indigo.[13] Voss et al.
demonstrated the possibility of preparing highly-soluble
indigo derivatives with alkoxy groups in the 4,4 and 7,7
positions via the Baeyer-Drewsen synthesis starting from
o-nitrobenzaldehyde substituted with two alkoxy
groups.[14,15] Meier and Lttke have reported several versatile routes to indigo with alkyl groups in the 5,5- and
6,6- positions.[16]
The reduction of indigoids is used in the vat dyeing
procedure. Since the dyes themselves are insoluble, they
are first reduced to the water-soluble leuco forms. The
leuco form of indigo is pale yellow. The now soluble
anionic dye easily penetrates into textile fabrics. Upon removal from the vat, the dye rapidly oxidises in air to
yield the coloured neutral indigo (Figure 2 a). In the industrial dyeing process, sodium dithionate is the most
commonly-used reducing agent. All indigoids exhibit
a characteristic electrochemistry of reversible two-electron reductions. Cyclic voltammograms of both indigo
and Tyrian purple in thin-film form are shown in Figure 2 b. It is not clear how the leuco form was produced
in ancient times: in some cases it is clear that zinc metal
was used, while in other cases yeast was added to make
fermentation vats.[13,8] The mystery of biblical Tekhelet
blue confused researchers for many years, as the Talmudic texts described the blue dye as being of shellfish
origin. However, Tyrian purple is purple, not blue. It was
known that the leuco form of Tyrian purple debrominates
upon exposure to sunlight, yielding the blue indigo.[17] It
is now believed that this is the most likely source of the
biblical blue.[18] An alternative explanation is that certain
snails might contain varying levels of bromo-free precursor, resulting in a large proportion of blue-coloured
indigo or 6-bromoindigo. Elsner and Spanier describe two
methods of blue-dyeing using molluscs of the species
Murex trunculus, one of which is based on the debromina-
Scheme 3. Preparation of asymmetrically-substituted indigoids by condensation of substituted 2-chloroindolone with indoxyl derivatives.
Isr. J. Chem. 2012, 52, 1 12
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Review
Figure 2. (a) Scheme of the reduction of indigoids during the vat dyeing process. (b) Cyclic voltammogram of indigo and Tyrian purple
40 nm thin films. The films were evaporated on indium tin oxide coated-glass, which functioned as the working electrode, with platinum
disk counter electrode and Ag/AgCl reference electrode, in 0.1 M TBAPF6 in CH3CN, 20 mV/s scan rate.
tion process.[19] Other indigoids, containing sulfur, oxygen,

or selenium rather than nitrogen heteroatoms, are also
colourants although these derivatives are yellow or red
(Figure 3 c).[2,3]
4 The Physical Chemistry of Indigoids

In 1908 Paul Friedlnder provided a general structural
definition of indigoids, as shown in Figure 3 a. The most
striking property of indigo and Tyrian purple is of course
the intense colour. It is surprising that a chromophore
with such a small conjugated p-network has such redshifted absorption. Normally much more extensive conjugation (e.g. phthalocyanines) or several powerful donor
and acceptor groups (e.g. substituted azo-compounds or
anthraquinones) are required to produce blue dyes. The
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explanation of the electronic absorption of indigo rests in

the high planarity of the molecule, which is enforced by
intramolecular hydrogen bonding. The planarity results in
a crossed-conjugated system.[20] The deep colour of indigo
is explained by the high polarisability of the electronic arrangement of the heteroatom diketo-diamino-ethylene
molecular centre. It was concluded in the work of Lttke
et al. that the chromogen of indigo is a doubly cross-conjugated system of two electron donor groups and two acceptor groups (Figure 3 b).[21] This conclusion was reached
through a combination of theoretical calculations and inventive syntheses of indigo analogues with different components stripped down.[21,22] Through their combination
of modelling and experiment, Lttke proposed the structure shown in Figure 3 b as the indigo chromophore. The
absorption peaks and extinction coefficients of different
indigoids are also shown in Figure 3 c.
Isr. J. Chem. 2012, 52, 1 12
Figure 3. (a) The general indigoid central unit initially proposed by Friedlnder in 1908. This structure remains correct today, though indigoids typically adopt the trans and not cis form. (b) The core indigo chromophore (so-called H-chromophore) as proposed by Lttke
et al.[21] (c) Optical absorption of different indigoids.
In the solid state, the absorption of indigo and Tyrian

purple is red-shifted by about 100 nm relative to dilute
solutions, demonstrating a strong intermolecular exchange coupling in the solid state. In both solid state and
in solution, indigoids exist in the trans form. The trans
isomer is maintained by intramolecular hydrogen bonding
between adjacent amine and ketone groups. For this
reason, unlike for example in thioindigoids (which lack
hydrogen bonding), photoinduced trans-cis isomerism is
never observed. Hydrogen bonding is responsible for
many key properties of indigoids. Solubility in organic
solvents is very low, with limited solubility in hot dimethyl sulfoxide or chloroform.[2,3,8] In the solid state, indigo
crystallises in the P21/c space group while Tyrian purple
crystallises in P21/a.[23,24] In both cases, each molecule is
hydrogen-bonded to four neighbours. Of those, two adjacent molecules are also p-stacked to each other. Thus p-p
interactions are reinforced by hydrogen bonds. The photophysics of indigoids are dominated by radiationless internal conversion. Fluorescence and intersystem crossing
occur in only low quantum yield. Internal conversion efficiency, fIC, is ~ 0.99 for both indigo and Tyrian purple.
The photoexcited state is thus deactivated without photoluminescence. Regardless of any substitution on the
phenyl rings, the photophysics of all indigoids remains the
same. It has been determined that the extremely short excited state lifetime and efficient internal conversion is
due to excited-state proton transfer followed by enol-keto
tautomerisation, depicted in Figure 4.[2,25,15] The excitedstate proton transfer mechanism has been reported in the
literature as leading to low fluorescence yields for other
compounds as well.[26]
Isr. J. Chem. 2012, 52, 1 12
Other indigoid derivatives with S, O or Se heteroatoms

are highly fluorescent.[2731] The same applies for indigoids
with acylated or alkylated amine nitrogens. In these molecules photochemical cis-trans isomerism is also observed.[2,3] The dye Cibalackrot, produced via the condensation of phenylacetyl chloride with indigo, is also highly
fluorescent.[32]
5 Organic Electronic Devices Based on Indigoids

Recently indigoids have been explored in organic electronics as natural and sustainable semiconductors.[6,33,34]
Thin films of indigo and Tyrian purple have been shown
to exhibit good charge transport properties. Both materials form highly-crystalline thin films upon evaporation.
When evaporated on aliphatic nonpolar substrate materials, indigo and Tyrian purple thin films show one sharp
peak in X-ray diffraction corresponding to the 100 and
001 planes, respectively. Thus the molecules are all in the
standing-up orientation. X-ray studies of indigo and
Tyrian purple deposited on organic field-effect transistor
(OFET) devices demonstrate a high degree of ordering
with no apparent amorphous domains and a single plane
developed in the growth direction. Contrary to typical organic semiconducting materials, where intermolecular interactions are limited to van der Waals forces and p-p interactions, indigoids additionally contain intermolecular
hydrogen bonding. This is likely the reason for the longrange ordering. Indigo and Tyrian purple also demonstrate a ~ 100120 nm bathochromic absorption shift from
dilute solution to solid state thin-films. This high ordering
is also reflected in the uncharacteristically high relative
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Review
Figure 4. The excited-state radiationless deactivation pathway of indigoids due to enol-keto tautomerisation. During the internal conversion, energy is dissipated through the rearrangement of the enol form to the thermodynamically-stable keto form. Internal conversion is
three orders of magnitude more efficient than radiative decay (kIC ~ 0.998 for indigo).
permittivity values of 4.3 for indigo and 6.2 for Tyrian

purple.
We fabricated organic field-effect transistor (OFET)
devices using only natural materials. The device schematic is shown in Figure 5. The substrate is made from the
natural resin shellac, a natural polyester produced by beetles in India and Southeast Asia. Shellac is readily processed from ethanol solution to form smooth (rms rough-
ness < 1 nm) substrates of any shape. Next an aluminium

metal gate electrode is evaporated. This electrode is electrochemically oxidised in a buffered citric acid electrolyte
solution to form a 45 nm thick Al2O3 gate dielectric. The
Al2O3 is then passivated with a 30 nm vacuum-evaporated
layer of tetratetracontane, TTC (C44H90), a waxy oligoethylene found in tropical plants.[6] 75 nm indigo or
Tyrian purple semiconducting layers are then evaporated.
Figure 5. Organic electronics with indigoids.[33,34] (top) The OFET device schematic. A W/L of 1 mm/80 mm was used for all devices shown
in this paper. (bottom) photo of a five-transistor sample on a shellac substrate.
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Isr. J. Chem. 2012, 52, 1 12
Figure 6. (a) Transfer characteristics of an indigo transistor with W/

L 1 mm/80 mm. Gate dielectric Al2O3 (45 nm) j TTC (30 nm), C0d =
87 nF/cm2. (b,c) Output characteristics in the first and third quadrants, respectively.
Gold source and drain electrodes are next evaporated

through a shadow mask with a W/L of 1 mm/80 mm to
form the source and drain electrodes. Interestingly, these
transistor devices exhibited ambipolar operation with
electron and hole mobilities in the 1020.2 cm2/V s
range. In a more recent work, higher mobilities in Tyrian
purple were reported, with electron and hole mobilities
of 0.4 cm2/Vs.[39] The ambipolarity of indigoids is correlated with the observation of reversible oxidation and reducIsr. J. Chem. 2012, 52, 1 12
Figure 7. (a) Transfer characteristics of an Tyrian purple transistor

with W/L 1 mm/80 mm. Gate dielectric Al2O3 (40 nm) j TTC (40 nm),
C0d = 43 nF/cm2. (b,c) Output characteristics in the first and third
quadrants, respectively.
tion electrochemistry (Figure 6, Figure 7). AFM studies of

both indigo and Tyrian purple show the growth of distinct
crystallites with sizes in the 200500 nm range.[33,34] With
a channel width of 80 microns, it is likely that hopping between grains is the mobility-limiting process. The key
semiconductor parameters of indigo and Tyrian purple
are summarised in Table 1.
Indigo devices showed stable p-type operation in air,
but no air-stable n-type operation was observed. We believe this is consistent with the high-lying LUMO level
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Review
Figure 8. Quasi steady-state output characteristics of an indigobased voltage inverter in the first quadrant (a) and third quadrant
(b). The inset schematic shows the voltage inverter circuit.
(3.8 eV), as oxygen acts as an electron acceptor.[35] We

found that exposure to the atmosphere over several
weeks, however, did not result in irreversible degradation.
Measuring devices in an inert environment after storage
in ambient air over the course of several months proved
that there was no deterioration of performance. The
LUMO level of Tyrian purple is deeper however, at
4.0 eV, and devices could be operated stably in air for
both p- and n-channels for at least 30 minutes with repeated cycling. The electron mobility was found to drop
by a factor of 2 during repeated cycling in air. To our
knowledge, in terms of low operating voltage, mobility,
Figure 9. Quasi steady-state output characteristics of Tyrian

purple-based voltage inverters in the first quadrant (a) and third
quadrant (b).
ON/OFF ratio and stability, these indigo-based OFET devices are among the best reported.[36,37] An interesting and
not yet fully-explained aspect of both materials is that
they only show semiconducting action on highly aliphatic
passivation layers, such as TTC or low-density polyethylene. From X-ray studies, it is apparent that these substrate materials induce a standing-up arrangement of the
Table 1. Band gap, HOMO and LUMO levels, mobilities and permittivity of indigo and Tyrian purple.
Material
Band Gap (eV)

CV estimate
Band Gap (eV) optical
HOMO (eV)
LUMO (eV)
Mobility (cm2/V s)
Relative permittivity (er)[a]
Indigo
1.7
1.7
5.5
3.8
4.3
Tyrian purple
1.8
1.9
5.8
4.0
me = 1 102
mh = 1 102
me = 3 102
mh = 0.2 (me, mh = 0.4)
6.2
[a] Relative permittivity is calculated from the geometric capacitance at high frequency (> 1 MHz). Loss angles in both materials: 1 103 at
1 MHz, 1 102 at 0.01 Hz.
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Isr. J. Chem. 2012, 52, 1 12
indigo molecules, leading to p-stacking parallel to the

substrate, and thus ideal of OFET charge transport. This
substrate-sensitive performance of OFETs is also observed in planar sandwich diodes, where depending on
the substrate, several order-of-magnitude differences in
current-voltage (I-V) characteristics are observed.[6]
The interest in ambipolar materials stems from the possibility of simple fabrication of complementary-type circuits.
Complementary
metal-oxide-semiconductor
(CMOS) integrated circuits form the basis of siliconbased electronic devices. Fabrication of an organic equivalent would require patterning n- and p-type materials on
neighbouring transistors, or creating a blend of hole and
electron-transporting materials. The use of a single ambipolar material is therefore a much simpler solution. Ideally, such a material should also have a small band gap, to
support injection of both carriers from a single electrode
metal. Indigo and Tyrian purple satisfy all these requirements. We have fabricated a simple NOT-logic voltage inverter. Output characteristics of quasi-steady state measurements of such inverters are shown in Figure 8 and
Figure 9. The voltage gains obtained for both materials
are among the highest reported in the literature for single
materials, with the gains in Tyrian purple devices being
the best reported to date.
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
6 Conclusions
Our recent work with indigoid dyes shows that very old
materials may show promise in designing novel organic
electronics devices. Indigo and Tyrian purple form highlyordered thin films that afford ambipolar charge transport
with relatively high mobilities. These materials show that
bio-inspired materials can compete with the best organic
electronic materials and in conjunction with other biomaterials (i.e. substrate, dielectric) they demonstrate the possibility of creating completely biocompatible/biodegradable electronics. As a previously unexplored family of
materials in organic electronics indigoids would also function as interesting building blocks in the synthesis of
larger molecules or polymers.[38] The ambipolar operation
of indigoids in OFETs is also significant, with Tyrian
purple being a prime candidate for air-stable organic electronic products.
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Received: October 17, 2011

Accepted: January 9, 2012
Published online: && &&, 0000
Isr. J. Chem. 2012, 52, 1 12

Indigo and Tyrian Purple - From Ancient Natural Dyes To Modern Organic Semiconductors

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