Solid State Communications, Vol. 90, No. 4, pp.

261-265, 1994
Pergamon Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0038-1098/94 $6.00 + .00

003S-~098(94)E0006-W

DEMBER EFFECT IN C60 THIN FILMS

Dipankar Sarkar and N.J. Halas
Department of Electrical and Computer Engineering and The Rice Quantum Institute, Rice University,
Houston, Texas, USA
(Received 4 November 1993 by A.A. Maradudin)

Photoinduced diffusion of charge carriers is observed in the form of a

potential difference across thin films of photoexcited C00. The
threshold photon energy for macroscopic separation of mobile charge
carriers in C00 is 2.3 4- 0.1 eV. This is also a conclusive demonstration
of the fact that the optical absorption at 2.3 eV is responsible for
electronic excitations across the C00 "bandgap". Experimental
evidence suggests a bimolecular process for charge transport and
carder dynamics in C60 solids. The polarity of the observed
photovoltage confirms earlier published results that the negative
charge carriers (electrons) are significantly more mobile than the
positive charge carders (holes) in C00 solids. The estimated mobility of
the electrons in C00 is ,-~ 1 cm2V -I s-1. The diffusion length for
electrons in C00 is estimated to be ,-, 10/~m.

THE DISCOVERY of methods to produce macro-
scopic quantities of fullerenes such as C00 [1] has
spurred considerable interest and effort in studying
the electrical properties of fullerene thin films [2-7].
There has been a large number of studies, both
theoretical and experimental, towards understanding
the solid state properties of C00. Specifically, there are
still ongoing controversies on properties like the
bandgap or the connection between the optical
absorption and the mechanisms for charge transport
in solid C00 [3, 7-1 5]. In fact, the threshold energy for
generation of free carriers has been the subject of very
recent studies [16]. In this paper we report the direct
observation of macroscopic charge separation (i.e.
electrons and holes) in solid C00 in response to
photoexcitation. The phenomenon observed is a
voltage generated across a thin film of C00 in
response to incident light and subsequent diffusion
of the charge carriers. This phenomenon is well
known in the semiconductor literature as the Dember
photovoltage, or the Dember effect [17-20].
The physics of the Dember effect is illustrated
in Fig. 1. Light is incident on one surface of a thin
C00 crystal. At time t = 0, electron-hole pairs are
formed in proportion to the light intensity, for low
(_< l mWcm -2) intensities, within an absorption
depth of the illuminated surface of the film.
261
Subsequently, the electrons and holes diffuse into
the film, each at their own rate, due to the concen-
tration gradient established by the attenuating light
intensity. It has been reported that electrons are very
mobile in C00 relative to the holes [4]. As a result, the
holes stay close to the generation site, while the
electrons diffuse out to distances of the order of the
diffusion length of electrons in C00. Under steady
state there is a net excess of positive charges close to
the illuminated electrode and negative charges close
to the dark electrode. This gives rise to a measurable
potential difference across the thin film where the
illuminated electrode is positive with respect to the
dark electrode.
The experimental setup is illustrated in Fig. 2. The
sample device was fabricated as follows: (a) Silver
was deposited, by vacuum evaporation from a
graphite crucible, onto a cleaned glass substrate,
2.5cm x 2.5 cm, to form the "bottom" or backplane
electrode, (b) Commercially available C00 was
sublimed in vacuum on top of the bottom electrode
to thicknesses in the range 1-20/Jm, and finally,
(c) using a shadow mask, silver was deposited on
the top to form the "top" or front plane electrodes.
The top electrode was made thin enough (100-300,~)
to be semi-transparent but sufficiently conducting.
A combination of a white light source and a
262 DEMBER EFFECT IN C6o THIN FILMS Vol. 90, No. 4
ELECTRON I HOLE E L E C r R O N I HOLE S
T ~ C60 lay~
GENEgATION 4 DISTRIBUTIONS
TiME>O

I so~c~ ~ ~ m _ I ~,d _v . ! I\
(ss~ _- 1
t--

ceos~ow¢. I /

Fig. 2. Experimental setup to determine the spectral

I_ J dependence, the intensity dependence and the
I- ~Rm -I I- c*o mua -I
Fig. 1. Dember effect: photodiffusion of carriers with
different mobilities result in a voltage across a thin
film of Co,0.
monochromator was used for the light source in the
experiments to determine the spectral response of the
photovoltage generated. An Ar + laser (488um line)
was used for the intensity and chopping frequency
dependence measurements. Electrical connections
were made from the top and bottom electrodes to a
lock-in amplifier to measure the photovoltage
generated across the sandwiched Ceo film. The Ce0
layer was made sufficiently thick to reduce complica-
tions due to diffusion of the top silver electrode into
the C60 film [21]. The experiments were performed in
air.
Figure 3 illustrates the spectral dependence of the
photovoltage. The photovoltage is normalized to the
intensity of the incident light at a given frequency.
For incident photons with energies greater than
2.3eV, the open circuit voltage across the film
increases very rapidly. This is strongly correlated
with the optical absorbance of C60 films [2, 22] which
also exhibits a sharp threshold at 2.3 eV. The optical
absorbance is also shown on the same plot as the
chopping frequency dependence of the Dember
photovoltage.
voltages. The weak peak in the Dember voltage in the
range 1.7-2.2 eV could be due to singlet and/or triplet
exciton annihilation and corresponds to weak optical
absorption in the same range [16].
Assuming that the concept of carrier transport in
bands is valid for C60 solids [10], electron-hole-pairs
(e.h.p.) would be generated for photon energies
greater than the bandgap of C60. Thermal excitations
would also contribute to an equilibrium thermally
generated population of electrons and holes in the
respective bands. Thus, under thermal equilibrium
conditions, the electron and hold densities should be
hi, the intrinsic carrier density at a given temperature.
In the presence of light, an additional population of
electrons and holes would occur. Since in equili-
brium, there would be no net time rate of change of
the carrier densities, it follows from the continuity
equation for charge that the generation rate must
equal the recombination rate [20]. Assuming a
bimolecular recombination mechanism to be valid
1.; i i
• x :
....... :...... ...... A B S O R B A ............

photovoltage and the correlation is clearly demon-

strated. There have been several experiments reported ~- :: ..... i .......... ~........... i .......... i....~.....i ........... i ...........

in the literature that demonstrated evidence for an i : : !i ! !

increase in photoconductivity in solid C60 and

photoactivity in C60 device structures close to the
2.3eV absorption threshold [2, 16, 23]. However,
since photoconductivity can occur by indirect
processes even in the absence of free carriers, such 0.',
......... ~................... *! ........... ~ ............ ~ ...... '::
E ,;, ...................
:"
as by exciton annihilation at the contacts to an
external circuit, such experiments are relatively ~'.6 ~.e 2 2.2 2.4 2.s 2.a 3 3.2
inconclusive about the nature of the conduction ENERGY(eV)
process. The presence of a Dember photovoltage, by Fig. 3. Spectral dependence of the Dember photo-
comparison, is an indication of the macroscopic voltage, illustrating a high correlation with the
separation of photoinduced charge carriers. A purely absorbance threshold at 2.3 eV. The Dember voltage
excitonic process would not lead to large Dember is normalized with respect to the intensity of the fight.
Vol. 90, No. 4 DEMBER EFFECT IN C6o THIN FILMS
3 " "
me~ i ai ~ ! i :
1.5-
. .......
• !
0.5
10 15
i
20 25 30 35
SQRT(INTENSITY,mW/cm^2)
Fig. 4. Intensity dependence of the Dember photo-
voltage illustrates (Intensity)1/2 dependence for
incident light intensities greater than 10mWem -2.
This indicates a bimolecular mechanism to be
responsible for the photovoltage.
for the electrons and holes (that is the recombination
rate is proportional to the product of the electron and
hole densities), the excess carrier densities would
follow the equilibrium relation [20]:
+ Gth,,, = A(n, + An)0,, + Ap),
where Gttffia~ and Gopti~ are the generation rates, A
is the recombination rate constant, and An and Ap
are the excess carrier densities. Also, nt =Pi and
An = Ap for an undoped material. Since G ~ = Vdmbcr then the maximum field inside the film is
Anlpl, we have Gop~cal= A[2n~An + (An)2]. Since
Gop~c~ is directly proportional to the intensity of
the light, the excess carrier densities would be
proportional to the light intensity for low intensities
(when An would be small and the square term could
be neglected). Dember photovoltage is proportional
to the density of excess carriers. Thus, the normal-
ization of the Dember photovoltage with respect to
the intensity is valid since the intensity of the light at
the output of the monochromator was only a fraction
of a milliwatt per cm2.
For higher light intensities ( 1 - 2 W c m -2) the
excess carrier densities could be much greater than
the thermally generated population and as a
consequence the excess carrier densities would be
proportional to the square root of the light intensity
(neglecting the first term). The intensity dependence
of the Dember voltage in the higher intensity regime
is illustrated in Fig. 4. This data is in agreement with
earlier published literature on the threshold intensity
for bimolecular recombination in C~0 solids [24]. An
Ar + laser was used in combination with a variable
neutral density filter and a chopper (chopping
frequency = 176Hz) to carry out this part of the
263
experiment. The square root dependence on intensity,
for the higher intensifies, is indicative of a bimol-
ecular process [24, 25]. This shows that the mechan-
ism for photovoltage generation is related to
macroscopic charge separation in solid C60.
For a bimolecular recombination process, the
magnitude of the response, the Dember voltage in this
case, should be inversely proportional to the square
root of the excitation (chopping) frequency [20, 24].
However, the f-l~2 frequency dependence is valid
under steady state so long as the electrons diffuse out
to distances that are comparable to the distances that
40 they can travel under carrier drift within one time
period of the optical excitation (l/chopping fre-
quency). For very fast chopping frequencies, the
electrons cannot diffuse across the entire sample
thickness before they recombine with the holes. This
implies a faster decrease in the Dember voltage with
increasing chopping frequencies. The cut-off point or
the knee in the response vs frequency plot could
therefore give us an estimate for the mobility of the
electrons in solid C60. If the cutoff" frequency is .fc,,
then it implies that the electrons are able to move
back and forth through the sample within a time of
(1)
l/for. If the sample thickness is d, and the mobility of
the electrons in solid C~0 is/~, then the time required
to move back and forth would be 2d/(/~E), where E is
the average electric field generated by the charge
carriers. If the magnitude of the Dember voltage is
Vdemb=/d.Estimating the time average electric field to
be half of this maximum, we arrive at an expression
for the mobility of the electrons:/z = 4d2f~/Vdemb~.
For a film thickness of 10/~m, and from the data in
Fig. 5 fc, " 300 Hz, the estimated mobility for the
electrons in C60 is ,,, 1 cm 2 V -~ s-~. This estimate is
within two orders of magnitude of the estimate
reported elsewhere from measurements of transient
photoconductivity [16]. However, this is still well
within the range of mobilities expected for a
molecular semiconductor [26]. Figure 5 shows the
chopping frequency dependence of the photovoltage.
A mechanical chopper was used to obtain modula-
tion frequencies in the range 70-2500 Hz. The light
source was again an Ar + laser (488nm line). The
frequency dependence shows f-U2 dependence for
low frequencies. Above for the response is seen to
decrease faster with increasing chopping frequency.
This data was obtained for a newly prepared sample.
For samples exposed to atmosphere for several days
there is deviation from the f - 1/2 dependence. Capaci-
tance and conductance measurements at different
frequencies yielded frequency dependent capacitance
and conductance for the devices indicating the
264 D E M B E R EFFECT IN C60 T H I N FILMS
0.4
O
i incidence of the light and attenuation within the film
.0.a
UJ
m
:E
ttJ -o.4
/
-o.
~:, =.° =.° ~ 3~ 3., 3.s
LOG(CHOPPINGFREQUENCY,Hz)
Fig. 5. The Dember photovoltage dependence on
chopping frequency illustrates f-1/2 dependence for
low frequencies. This also indicates a bimolecular
recombination mechanism to be valid for the
photovoltage generation process. The cutoff fre-
quency gives an estimate for the mobility to be
1 cm2V-I s -I"
formation of bulk and surface traps with very large
lifetimes (~ 0.1 s) [27]. The presence of such traps
could affect the frequency dependence of the
measured voltage.
When the incident photon energies are close to
2.3 eV, the absorption depth for the incident light is
approximately a few hundred nanometers [22]. Thus,
for films whose thicknesses are comparable to a few
absorption depths of the light, the thicker the film,
the larger would be the generated photovoltage since
there would be relatively more charge separation for
a thicker film (the electrons can diffuse out to longer
distances), as illustrated in Fig. 1. However, when the
film thicknesses are in excess of several diffusion
lengths (the thick film regime), the net charge
separation would be smaller for thicker samples
since the diffused electrons would ultimately recom-
bine within a few diffusion lengths. In our experi-
ments, both the polarity of the photovoltage and the
thickness dependences described above are observed,
confirming the mechanism of photovoltage as due to
photo generation and subsequent diffusion of charge
carriers. For our samples the thick film regime
behavior is observed when film thicknesses are
10 pm or higher. From this we estimate the diffusion
length of the electrons in C60 to be ~ 10/~m, which is
consistent with other experiments reported on carrier
drift (in the presence of an electric field) in C60 thin
films [4]. As an additional proof, when we illuminate
both the surfaces of the thin film, with samples
prepared on glass substrates, the generated voltage is
reduced, and is consistent with the hypothesis that it
Vol. 90, No. 4
is the anisotropy introduced by the direction of
that is responsible for the photovoltage. Current-
voltage characteristics on these devices demonstrated
sufficiently ohmic (linear) behavior, indicating the
absence of schottky barriers at the contacts that
could also generate a photovoltage. Possible compli-
cations due to diffusion of silver into C60 prevented
the measurement of temperature dependence of the
Dember photovoltage [21].
The magnitude of the Dember photovoltage
depends on several factors in general. All factors on
which the net charge separation is dependent, such as
the surface recombination velocities at the two
surfaces, the surface and bulk trap distributions and
their cross sections and the diffusion length or
lifetime of the free carriers, are collectively respon-
sible for the exact magnitude of the generated
voltage. As some of these numbers are not yet
precisely known, the measured Dember voltage
magnitude is of limited utility. In our samples the
magnitude of the voltage ranged from 1-100mV for
a range of sample thicknesses from 5000 A to 40/~m.
The existence of the Dember effect in C60 thin
films which we have reported is evidence for
the photoinduced generation of free carriers in C60
solids. This measurement is independent supporting
evidence that the transition at 2.3 eV corresponds to
the excitation of free carriers across a bandgap.
Acknowledgements - The authors would like to
acknowledge support from the Robert A. Welch
Foundation, the Texas Advanced Technology Pro-
gram, and the Office of Naval Research. NJH is a
recipient of an NSF Young Investigator Award.
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