LETTERS TO NATURE

10- 7 S m 2 r' for H 2 P and ZnP respectively at room temperature. maximum jump times of 0.6 and 2 ps for solid ZnP at room
The presence of the central zinc atom therefore seems to increase temperature and the mesophase at 100 °C, respectively.
the conductive properties of the solid slightly. Our results confirm that the transport of charge can occur
In Fig. 2, (6.u/ D) 0 is plotted as a function of temperature. very rapidly within an organized self-assembly of porphyrin
For H 2 P, a single, sharp decrease occurs at the transition from moieties even in a relatively fle xible, liquid crystalline phase.
the solid to the isotropic liquid. No conductivity could be Such peripherally hydrocarbon substituted compounds may
detected in the isotropic phase. For ZnP, the conductivity therefore be considered to provide model systems which
decreases abruptly, but does not disappear completely, at the crudely mimic the channelling of energy and charge found in
solid to liquid-crystal transition temperature. The conductivity the highly varied antenna chlorophyll arrays of photosynthetic
in the mesophase is a factor of - 3 less than in the solid with membranes. 0
(6.u/ D) 0 = 0.5 x 10- 7 S m 2 r 1 • This increases slightly with fur-
ther increase in temperature in the mesophase and then suddenly Received 9 July; accepted 13 September 1991.
drops to zero at the clearing point of ZnP. 1. Gregg, 8. A .. Fox, M. A. & Bard, A. J. J. Am. chem. Soc.. 111, 3024 - 3029 (1989).
We conclude that the long-range columnar order of porphyrin 2. Weber, P., Gurllon. D. & Skoulios, A. Liq. CrysL 9, 369-382 (1991).
moieties in the solid and liquid-crystalline phases is essential 3. Warman. J. M. & de Haas. M. P. in Pulse Radiolysis. Ch. 6 . (ed. Tabata, Y.) 101- 133 (CRC, Boca
Raton, 1991).
for the conductive properties observed. In the isotropic liquid 4. Warman, J. M. & de Haas, M. P. Radiat. Phys. Chem. 34, 581- 586 (1989).
phase, any molecular organization that might occur must be of 5. Eley, D. D. Malec. Crysl. Liq. Cryst. 171, 1 - 21 (1989).
6. Simon, J. & Anore, J-J. Molecular Semiconductors (Springer, Berlin. 1985).
such a limited temporal or geometrical extent that it cannot 7. Pietro, W. J.. Marks, T. J. & Ratner, M. A. J Am. chem. Soc. 107, 5387- 5391 (1985).
support charge conduction. The results provide definitive 8. Warman, J.M., de Haas,M. P., van der Pol, J. F. & Drenth, W. Chem. Phys. Letr. 164, 581 - 586 (1989).
9. Warman, J M. in The Study of Fast Processes and Transient Species by Electron Pulse Radiolysis
evidence, therefore, for the general supposition that electrons (eds Baxendale, J. H. & Busi, F.) 433- 533 (Reidel, Dordrecht, 1982).
and/ or holes can move rapidly along the axis of column-stacked 10, Schmidt. W. F. & Allen, A. 0 . J Phys. Chem. 72, 3730- 3736 (1968).
7T-systems 5 •6 • The decrease in conductivity on going from the 11. Shinsaka, K. & Freem an, G. R. Can. J. chem. 52, 3495 - 3506 (1974).
12. Cox, C. A. & Knight, P. C. J Phys. C. 7, 146- 156 (1974).
crystalline solid to the mesophase is attributed to a lower charge 13. rv1ott. N. F. Conduc tion in Non-Crystalline Materials. Ch. 6 (Clarendon. Oxford. 1987).
mobility. This is probably due to an increase in positional
ACKNOWLEDGEMENTS. We thank M. Northolt and S. J. Picken (AKZO Research Laboratories, Arnhem)
disorder of the porphyrin moieties 7 on melting of the hydrocar- for X-ray diffraction analysis of the ZnP compound and for helpful discussions. The synthetic work
bon mantle. was sponsored by the Texas Advanced Technology Program.

We have found a similar decrease in the radiation-induced

conductivity at the solid to mesophase transition of octa-alkoxy-
substituted phthalocyanines. An isotropic liquid phase of these
compounds is n ot, however, attainable within the temperature
A low-cost, high-efficiency solar
range of our equipment. They could not therefore be used to
carry out the conclusive experiment of completely melting the
cell based on dye-sensitized
material to see if long-range order was essential for conduction.
The experiments on octa- n-alkoxy substituted phthalocya nines
colloidal Ti02 films
have, however, shown that the lifetime of the conductivity Brian O'Regan* & Michael Gratzelt
transient increases exponentially with the length of the alkyl
tails 8 . This is taken to be strong evidence that the mobile charge Institute of Physical Chemistry, Swiss Federal Institute of Technology,
carriers responsible are restricted to rapid diffusional motion CH-1015 Lausanne. Switzerland
along the phthalocyanine axis of a stack, with eventual charge
recombination requiring stack-to-stack electron tunnelling THE large-scale use of photovoltaic devices for electricity gener-
through the hydrocarbon mantle. ation is prohibitively expensive at present: generation from existing
The absolute value of (6.u/ D ) 0 is related to the mobilities, commercial devices costs about ten times more than conventional
µ. , of the charge carrers, L µ. = (µ.( - ) + µ. ( +) ), and the average methods 1• Here we describe a photovoltaic cell, created from low-
energy required to produce one charge-carrier p air, EP (in eV), to medium-purity materials through low-cost processes, which
by3·4 exhibits a commercially realistic energy-conversion efficiency. The
device is based on a 10-µm-thick, optically transparent film of
(I)
titanium dioxide particles a few nanometres in size, coated with
For orga nic compounds, the total initial yield of electron-hole a monolayer of a charge-transfer dye to sensitize the film for light
pairs corresponds to .a value of EP of -25 eV for high-energy harvesting. Because of the high surface area of the semiconductor
radiation 9 - 11 • Only a fraction of the initial electrons and holes film and the ideal spectral characteristics of the dye, the device
will escape rapid (subnanosecond ) geminate recombination 8 •9 harvests a high proportion of the incident solar energy flux ( 46%)
and diffuse to separate columns, thus being observed in the and shows exceptionally high efficiencies for the conversion of
present experiments. Using a value of EP = 25 eV together with incident photons to electrical current (more than 80%). The overall
the experimentally determined value of (6. u/ D) 0 will therefore light-to-electric energy conversion yield is 7.1-7.9% in simulated
yield a lower limit to the charge-carrier mobilities. For the solid solar light and 12% in diffuse daylight. The large current densities
phase of ZnP at room temperature, assuming electrons and holes (greater than 12 mA cm- 2 ) and exceptional stability (sustaining
to have almost equal mobilities 12, this gives µ. > at least five million turnovers without decomposition), as well as
2.6 x 10- 6 m 2 y - t s- 1 and for the mesophase, it gives µ. > the low cost, make practical applications feasible.
0.6 x 10- 6 m 2 v-• s- •. Solar energy conversion by photoelectrochemical cells h as
This order of magnitude of the mobility indicates small been intensively investigated 2 - 11 • Dye-sensitized cells differ from
polaron motion 13 corresponding to the hopping of a more or the conventional semiconductor devices in that they separate
less localized charge between neighbouring sites with an average the function of light absorption from charge carrier transport.
jump time between sites of Ti . The mobility measured in the In the case of n -type materia ls, such as TiO 2 , current is generated
present, randomly orientated columnar materials is related to when a photon absorbed by a dye molecule gives rise to electron
Tj by injection into the conduction band of th e semiconductor, Fig.
l. To complete the circuit, the dye must be regenerated by
(2)
where di is the distance moved along the columnar axis per
j ump (4.9 A for the present systems). The minimum values of • Present address: Department of Chemistry. University of Washington, Seattle. Washington 98195.
USA.
the carri er mobilities given above correspond therefore to t To whom correspondence should be addressed.

NATURE · VOL 353 · 24 OCTOBER 1991 737

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 LETTERS TO NATURE

electron transfer from a redox species in solution which is then easily. Films of 10 µm thickness consisting of particles with an
reduced at the counter electrode. The monochromatic current average size of 15 nm gave linear photocurrent response up to
yield full sunlight and were used throughout. A cubic close packing
of 15-nm-sized spheres to a 10-µm-thick layer is expected to
7/ i(A ) = LHE(A) X <Pinj X 7/e (1)
produce a 2,000-fold increase in surface area.
where LHE (light harvesting efficiency) is the fraction of the Absorption spectra obtained for such nanostructured TiO 2
incident photons that are absorbed by the dye, <Pinj is the quan- films are shown in Fig. 3. Bare films are transparent and colour-
tum yield for charge injection and 7/e is the efficiency of collecting less, displaying the fundamental absorption edge of anatase
the injected charge at the back contact, expresses the ratio of (band gap 3.2 eV) in the ultraviolet region. Deposition of a
measured electric current to the incident photon flux at a given monolayer of the trimeric ruthenium complex 15 ·16 , RuL 2 (µ-
wavelength. The photovoltage ~ V in Fig. I, generated by the (CN) Ru ( CN) L;) 2 , 1, where Lis 2,2' bipyridine-4,4' -dicarboxylic
cell , corresponds to the difference between the Fermi level in acid and L' is 2,2'-bipyridine, results in deep brownish-red
the semiconductor under illumination and the Nernst potential coloration of the film. The absorption onset is shifted to 750 nm,
of the redox couple in the electrolyte. the light harvesting efficiency reading almost I 00% in the whole
Although attempts to use dye-sensitized photoelectrochemical visible region below 550 nm . Integration of the spectral overlap
cells in energy conversion have been made before, the efficiency between a solar emission of AM 1.5 and this absorption band
of such devices has been extremely low and practical applica- shows that 46% of the incident solar energy flux is harvested
tions have seemed remote . One problem is that of poor light by the dye coated film (AM= 1/ sin a where a is the angle of
harvesting. On a smooth surface, a monomolecular layer of incidence of the solar rays at the Earth's surface ),
sensitizer absorbs less than l % of incident monochromatic light. The optica l density of the film at 478 nm corrected for the
Attempts to harvest more light by using multilayers of dye have absorption by the conducting glass support was 2.45. Dividing
in general been unsuccessful. The remaining option is to increase by the extinction coefficient 16 of I ( e478 = L88 x 10 7 cm 2 mol - 1)
the roughness of the semiconductor surface so that a larger yields the dye surface concentration, r = 1.3 x 10- 7 mol cm - 2 ,
number of dye molecules can be adsorbed directly to the surface As each dye molecule occupies an area 16 of I nm 2, the inner
and can simultaneously be in direct contact with the redox surface of the film is 780 cm 2 for each I cm 2 of geometric surface,
electrolyte. Matsumura et al. 12 and Alonso et al. 13 have used Thus, the roughness factor is 780, which is smaller than the
sintered ZnO electrodes to increase the efficiency of sen sitization predicted value of 2,000. The difference is attributed to necking
by rose bengal and related dyes. Willig, Parkinson and col- between TiO 2 particles. In addition , the large si ze of I prevents
leagues14 have reported high quantum yields for the dye sensitiz- its access to very small pores, reducing the apparent surface area.
ation of SnS 2 . But the conversion yields from solar light to The photocurrent action spectrum obtained with the dye-
electricity remained well below l % for these sys tems. In addition, coated TiO 2 film is also shown in Fig. 3. It closely matches the
the instability of the dyes employed presented a severe practical absorption spectrum, indicating that the current is due to elec-
drawback. By using semiconductor films consisting of tron injection from I into the conduction band of TiO 2 , The
nanometer-sized TiO 2 particles, together with newly developed photocurrent yield measured at 520 nm was found to depend
charge-transfer dyes, we have improved the efficiency and stabil-
ity of the solar cell.
High-surface-area TiO 2 films were deposited on a conducting
glass sheet from colloidal solutions . A transmission electron
micrograph of the colloid is shown in Fig. 2. Electronic contact
between the particles was produced by brief sintering at 450 °C.
The size of the particles and pores making up the film is control-
led by the size of the particles in the colloidal solution. The
internal surface area of the film is determined by the size of the
particles and the thickness of the film. These parameters were
optimized to obtain efficient light harvesting while maintaining
a pore size large enough to allow the redox electrolyte to diffuse
semiconductor dye electrolyte conducting glass
counterelectrode
............ . .
E /< (S+/S' )...................... / .•.·••·.· •·t·•·•·•
··~ ···.··.·.· ... · .· . . ·.···

- (~1#
>>(s+;s) · ·
FIG. 2 Transmission electron micrograph of Ti0 2 particles used in thin film
production. The scale bar represents 10 nm. Particles were prepared by
hydrolysis of titanium tetraisopropox ide1 8 ·19 foll owed by autoclaving for 12 h
at 200 °C. To form films the sol was concentrated by evaporation of water
load in vacuum at 25 °C until a viscous liquid was obtained. Carbowax M-20,000
(40% by weight of Ti0 2 ) was added and the viscous dispersion (Ti0 2 content
20% by weight) was spread on the conducting glass support (Asahi glass.
fluorine-doped Sn0 2 overlayer, transmission 85% in the visible, sheet resist-
ance BO/ square ) to give a membrane of 10 µm thickness . This was heated
FIG. 1 Schematic representation of the principle ot the dye-sensitized under air for 30 min at 450 °C. High-resolution scanning electron microscopy
photovoltaic cell to indicate the electron energy level in the different phases. revealed Ti0 2 films to be composed of a three-dimensional network of
The cell voltage observed under illumination corresponds to the difference, interconnected nanoscale particles 1 9 . Transmission electron micrographs
a V, between the quasi-Fermi level of Ti0 2 under illumination and the of Ti0 2 particles were taken before heat treatment; the annealing of 450 °C
electrochemical potential of the electrolyte. The latter is equal to the Nernst did not induce significant changes in particle size. Before dye coating, a few
potential of the redox couple (R/R -) used to mediate charge transfer between monol ayers of Ti0 2 were electrodeposited onto the colloidal Ti0 2 film from
the electrodes. S, sensitizer; S*, electronically excited sensitizer; s+,oxidized a Ti (III ) solution. Detailed description of this procedure will be published
sensitizer. elsewhere (L. Kaven, B.O'R., A. Kay and M.G., manuscript in preparation ).

738 NATURE · VOL 353 · 24 OCTOBER 1991

© 1991 Nature Publishing Group
 LETTERS TO NATURE
1 4
on the counter ion of the iodide/triiodide redox electrolyte, a
increasing from 68% for tetrapropylammonium to 84% for Li+. •. . 2
After correction for the light absorption by the conducting glass,
the yields are 80% and 97%, respectively. This shows that the 0

nanostructured TiO 2 films used in conjunction with suitable

charge transfer dyes can achieve quantitative conversion of 0 8

visible light photons into electric current.

0 6
Figure 4 shows the current-voltage characteristics obtained
with the thin layer cell under illumination by simulated AMl.5 0 4
solar light. The conversion efficiencies for one tenth and full
sunlight are 7.9% and 7.12%, and the fill factors (maximum
output power of cell~ [short circuit current x open circuit vol- "'E
Cl
0 2

tage]) are 0.76 and 0.685, respectively. Similar yields were <( 0 0
E o. 7
obtained under direct sunlight (measurements performed in 0 0 0. ~ 0 .2 0 .3 0 .4 0 5 0 6

June early in the afternoon on the roof of the institute). Under c

e • 2
b
diffuse daylight the efficiency increased to 12%, indicating that :i
Cl
under such conditions the cell performance is better than that 0
0 10
of conventional silicon devices. This is because the spectral .c
Q.
distribution of diffuse daylight overlaps more favourably with
the absorption spectrum of the dye-coated TiO 2 film than direct
sunlight. The fill factor of the cell remains above 0.7 even at
very low light intensity ( < 5 W m- 2 ) . Conventional photovoltaic
cells have a much smaller fill factor ( < 0.5) under these condi-
tions. This indicates that loss mechanisms such as recombina-
tion, normally encountered in semiconductor photoconversion,
have been minimized. This result might appear surprising in
view of the disordered structure of our film giving rise to defects.
But the role of the semiconductor in a dye-sensitized device is
0 0 0 1 0.2 0 3 0 4 0 5 0 .6 0 7
merely to conduct the injected majority charge carriers. There
are no minority carriers involved in the photoconversion process. Cell potential (V)
Therefore, surface and bulk recombination losses due to lattice
FIG. 4 Photocurrent- voltage characteristics of a cell, based on a col loidal
defects, encountered in conventional photovoltaic cells, are not Ti02 film sensitized by 1; the film, supported on a conducting glass sheet,
observed in such a device. was used in a sandwich-type configuration. The size of t he dye coated Ti02
The long-term stability of cell performance was tested by photoanode was 0.5 cm 2 . The counterelectrode, consisting of conducting
illuminating the thin TiO 2 film loaded with 1 with visible (A > glass coated with a few monolayers of platinum, was placed directly on top
400 nm) light for 2 months. The change in the photocurrent was of the working electrode. A thin layer of redox electrolyte is attracted into
less than 10% over this period, during which a charge of the intra-electrode space through capillary forces. The cell was exposed to
62,000 C cm - 2 was passed through the device, corresponding to simulated sunlight with AM1.5 spectral distribution. a, light intensity
a turnover number of 5 x 106 for the sensitizer. This implies that 83 W m- 2 , electrolyte: 0.5 M tet rapropylammonium iodide +0.04 M iodine
in a mixture of ethylene carbonate (80% by volume) with acetonitrile. Fill
if any dye degradation had occurred its quantum yield ( </>,ec) is
factor was 0.76; surface area 0.5 cm 2 (before multiplicat ion by roughness
less than 2 X 10- 8. As <Pctec = kdccl"I.k, the rate constant, kdec S- 1, factor). Conversion efficiency was 7.9%. b, light intensity 750 W m- 2 , elec-
for excited-state decomposition (due to processes such as ligand trolyte: 0.5 M tetrapropylammonium iodide, 0.02 M Kl x0.04 M 12 in the same
Joss) must be at least 10-8 times smaller than "I.k, the sum of solvent. Fill factor was 0.684; conversion was 7.12%.
rate constants for all channels of dye deactivation. Because
charge injection is the predominant channel, this sum is practi-

cally equal to the rate constant for charge injection, which

1.0
•
•• exceeds 1012 s- 1 in the case of 1. Therefore, the upper limit for
kctec is 2 x 104 s- 1 , which agrees with the known photophysics of
0.80 this class of transition metal complexes 17 . The very fast electron
injection observed with dyes such as 1, combined with high
I
chemical stability, renders these compounds very attractive for
0 .60 ~ practical development. D
u>-
C
Q)

~
w OJ B

l Received 19 July: accepted 20 August 1991.

l. Bucher, K. & Fricke, J. Phys. Zeit 21, 237- 244 (1980).
2. Honda. K. & Fujishima, A. Nature 238, 3 7- 39 (1972)

j 300 400 500 600 700 800

3.
4.
5.
6.
7.
8.
Tufts. 8. J. et al. Nature 326, 681- 683 (198 7).
Gerischer, H. Electrochim. Acta 35, 167 7 (1 990).
Licht, S., Hodes. G., Tenne, R. & Manassen. J. Nature 326, 863- 8 64 (1987).
Heller, A. Acc. chem. Res. 14, 154- 162 (1981).
Nozik, A. J. Phil. Trans. R. Soc. Land A295, 453- 470 (1980).
Tributsch, H. & Bennet. J. C. 1 electroanal. Chem. 81, 9 7 (1977).
9. Wrighton, M. S. Acc. chem. Res. 12, 303 - 310 (1979).
Wavelength (nm)
10. Bard, A. J. Science 207, 139 11980).
FIG. 3 Absorption and photocurrent action spectra of Ti02 films supported 11. Memming, R. Phil. Tech Rev. 38, 160 (1979 ).
1 2. Matsumura, M., Nomura, Y. & Tsubomura, H. Bull. chem. Soc. Japan 50, 2533 (1977).
on conducting glass. A, absorption efficiency of the bare Ti02 film corrected 13. Alonso, N., Beley, V. M , Chartier, P. & Em, V. Rev. Phys. Appl. 16, 5 (1981).
for conducting glass background; B, absorption efficiency of the same film 14. Willig, F., Eichberger, R., Sundaresan, N. S . & Parkinson. B. A. 1 Am. chem. Soc. 112, 270 2 - 2707
coated with a monolayer of 1; full circles, monochromatic current yield at (1990).
15. Amadelli, R., Argazzi, R., Bignozzi, C. A. & Scandola, F. 1 Am. chem. Soc. 112, 7099-7103 (1990).
short circuit as a function of excitation wavelength. Yield is corrected for
16. Nazeeruddin, M. K., Liska, P., Moser, J., Vlachopoulos, N. & Gratzel. M. He/v. chim. Acta 73,
15% loss of incident photons through light absorption and scattering by 1788- 180 3 (1990 ).
the conducting glass support. 17. Juris, A.. Balzanr. V.. Barigletti. F.. Campagna, S.. Belzer, 8. Coard Chem. Rev. 84, 85 (1988).

NATURE · VOL 353 · 24 OCTOBER 1991 739

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 LETTERS TO NATURE
18. Anderson, M. A., Gieselmann, M. J. & Xu, Q. J. Membrane Sci. 392, 43 (1988). The spiral wave dynamics were followed with a video recorder
19. O'Regan, B., Moser, J., Anderson, M. & Gratzet, M. J phys. Chem 94, 8720-8726 (1990).
connected to a PC computer. To observe super-spiral waves,
ACKNOWLEDGEMENTS. We are grateful to !. Rodicio for experiment al help, to M. Nazzeruddin for a simple image processing was carried out : after acquiring two
sample of sensitizer and to A. Kay for advice on the preparation of colloidal membranes. This work
was supported by the Swiss National Energy Office.
successive images (separated by 2 min ), we subtracted the second
from the first. This same procedure was used in the calculations
of ref. 11. Contrast enhancement was then used to improve the

Super-spiral structures in an
quality of the printed pictures.
Spiral waves with many turns were created by the following
excitable medium procedure: at the beginning of the experiment, the sulphuric
acid concentration was reduced (to -0.2 M) to avoid the spon-
V. Perez-Muiiuzuri*, R. Aliev, B. Vasiev, taneous appearance of wave sources. Spiral waves were pro-
duced in this medium by the breaking of a circular wave. To
V. Perez-Villar* & V. I. Krinsky increase the frequency and the number of spiral turns, sulphuric
Institute of Theoretical and Experimental Biophysics,
acid was added until it reached its final concentration (0.5 M ).
Academy of Sciences USSR, 142292 Pushchino, Moscow Region, USSR This procedure made it possible to create a single vortex of
* Departamento Fisica de la Materia Condensada, Facultad de Fisicas, -14 turns, with period T, = 94 s and wavelength A,= 0.34 cm
E-15706 University of Santiago de Compostela, Spain (Fig. I ).
After the medium had become homogeneous, the spiral waves
ROTATING spiral waves have been observed in various excitable were perturbed by switching the current on and off. This resulted
media, including heart muscte1, retinae2, cultures of the slime in the successive increasing and diminishing of the size of the
mould Dyctiostelium discoideum 3 •4 and chemical oscillators such core 12, so that the spiral tip described a 'flowerlet' pattern. The
as the Belousov-Zhabotinsky (BZ) reactionS-7 • Under certain con- ratio of two frequencies associated with this motion was about
ditions the spiral wave does not exhibit simple periodic rotation, six.
but quasiperiodic8 (or 'compound' 9 ) rotation, in which the spiral's When this highly meandering tip motion occurs, the spiral
origin (the tip) meanders 10. Recent calculations 11 have shown that shape becomes asymmetric. Some of the wavefronts that make
highly meandering tip motion can impose superstructures on spiral up the spiral approach each other (see Fig. 2a ). When the picture
waves. Here we reproduce these patterns experimentally, using the is processed by subtracting one image from another, a su per-
BZ reaction as the excitable medium. We induce high tip meander structure appears with the shape of a spiral wave (Fig. 2b ). This
by applying pulses of electrical current locally at the tip 12 • Image super-spiral does not disappear with time, but rotates as the
processing of the patterns reveals a spiral wave of larger wavelength base spiral does; the tips of both spirals always coincide ( Fig.
superimposed on the original wave, an effect that can be described 3). Note that the same results were observed numerically 11
in terms of a Doppler shift in the original spiral. (compare upper and lower parts of Fig. 2).
All our experiments were performed in a BZ reaction 13 The period and wavelength of the super-spiral ( T,, = 540 s
in silica gel at room temperature (20 °C). A 0.9-mm-thick gel and Ass = 2 cm) proved to be six times as great as those of the
layer containing ferroin (0.008 M) was prepared in a Petri dish. base spiral. In contrast, the linear velocity was roughly equal
During the experiments this layer was covered with a thick for both spirals.
(6- 8 mm) solution of the other BZ reaction components: The super-spiral can be considered to be the result of the
0.1 M NaBrO 3 , 0.1 M CH 2 (COOH) 2 and 0.5 M H 2 SO4 • approach between fronts of the base spiral. In this case, the
The highly meandering tip motion needed for the production wave period detected at any point in the medium changes
of superstructures was enhanced by using stepwise pulses of periodically with time. Figure 4a shows this effect, measured at
electric current 12 with a period of 11 min. In each period, the a point near the centre of Fig. 2a.
voltage (1.5 V, -5 mA) was switched on for 4 min. The results presented in Fig. 4a can be interpreted by the
The electrical circuit used (analogous to that in ref. 12) Doppler effect. If we suppose that the waves of the spiral are
included two electrodes immersed in the liquid layer. One of emitted by a source rotating around a circle at constant velocity
these was a circular electrode which ran around the border of v1 and period T,,, then the period of waves at any point in the
the Petri dish, the other was needle-shaped (0.6 mm diameter) . medium is given by the equation
The needle was placed over the spiral tip (3 mm into the liquid
layer). Two different types of electrodes, stainless steel and T(t)= T,{1+ !::.!.cos(21r_:__+ ¢ )} (l )
platinum, were used, with the same results. v0 T,,

FIG. 1 Rigidly rotating spiral waves (a) for t he phase-reaction/ diffusion The appearance and behaviour in the two cases are strikingly similar:
equation, d'l'/dt = R{1- 15 sin (\I')} +aV 2 '1' +f31V 'l' l2 (refs 11 and 15; and P. constant wavelength, sharp fronts and rigid rotation around the centre. The
Hanusse and V.P.M., manuscript in preparation) and (b) in the BZ reaction. black spot in the centre of b is the electrode shadow.

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