APPLIED PHYSICS LETTERS 88, 133501 2006

Schottky diodes from asymmetric metal-nanotube contacts

Chenguang Lu, Lei An, Qiang Fu, and Jie Liua
Department of Chemistry, Duke University, Durham, North Carolina 27708
Hong Zhang and James Murduck
Northrop Grumman Corporation, Electronic Systems, 1212 Winterson Road, MS3B10 Linthicum, Maryland
21090
Received 4 March 2005; accepted 7 March 2006; published online 29 March 2006
Carbon nanotube Schottky diodes were fabricated using asymmetric metal-nanotube contacts. These
devices were prepared from semiconducting single-walled carbon nanotubes contacted by one Al or
Ti electrode and one Au electrode. Nanotubes formed a low resistance contact with the Au electrode
and a Schottky contact with the Al or Ti electrode. Electronic transport through the Schottky barriers
was determined by the competition between tunneling and thermionic emission, which could be
tuned by a back gate voltage. 2006 American Institute of Physics. DOI: 10.1063/1.2190707

Carbon nanotubes, especially single-walled carbon nano-
tubes SWNTs, are considered promising materials for
next-generation electronic applications.1 Many prototypical
devices have been fabricated using carbon nanotubes, includ-
ing field-effect transistors FETs,24 diodes,57 single-
electron transistors,8 nanoelectrodes,9 and several others.
Nanotubes also possess properties, such as high carrier
mobility,10 long mean free path,4 and capability of carrying
high current density,11 that rival or exceed currently used
materials, allowing researchers to develop unconventional
device structures to achieve better performance or explore
the limits of traditional designs.
However, more understanding and control are still
needed to integrate carbon nanotubes into complicated cir-
cuits. Along with the difficulty of controlling the types, lo-
cations, and orientations of SWNTs, a lack of understanding
of the contact between carbon nanotubes and macroscopic
metal electrodes is a critical issue. The formation of a
Schottky barrier between metal electrodes and nanotubes in-
creases device resistance and is generally considered a prob-
lem for device performance. Several groups have tried to
solve this problem by using high work function metals as
contact electrodes4 and by device annealing.12 However, a
barrier between metal electrode and semiconductor is desir-
able in certain applications, such as Schottky diodes used in
radio frequency rf engineering. Given their intrinsically
small capacitance, carbon nanotubes could be a promising
material for rf microwave applications.13
Schottky barriers at metal and carbon nanotube contacts
have been studied extensively. FETs made with single-walled
carbon nanotubes were found to be Schottky barrier devices
with functional parts at the contacts.2 Schottky diodes have
also been created with a scanned gate,7 between crossed
nanotubes,6 and on intramolecular junctions.14 However,
studies on Schottky barriers formed between SWNTs and
different metals are new and limited.1517 In this study, we
fabricated nanotube Schottky diodes using asymmetric metal
contacts. This type of device allows us to explore metal-
SWNT contact properties directly. Low work function met-
als, i.e., Al and Ti, were shown to be able to form Schottky
a
Author to whom correspondence should be addressed; electronic mail:
j.liu@duke.edu
barriers at their junctions with semiconducting SWNTs. We
also found that device behavior is determined by competition
between tunneling current and thermionic emission TE cur-
rent through the Schottky barrier. A back gate voltage can
tune this competition, while TE current dominates at more
positive gate voltages and tunneling current dominates at
more negative voltages. This tunability arises mostly from
the sensitivity of the tunneling currents to the back gate volt-
ages.
The device fabrication process started with chemical va-
por deposition CVD growth of SWNTs on SiO2 / Si wafers
Silicon Quest International, Santa Clara, CA. Solution syn-
thesized Fe/ Mo nanoparticles18 were dropped and dried on
the wafer and served as a catalyst. Transmission electron
microscopy TEM grids Ted Pella Inc., Redding, CA were
used as shadow masks to deposit aluminum or titanium pads
with a thickness of 50 60 nm as the first electrode. An
e-beam evaporator SOLUTION Process Development
System, CHA Industries, Fremont, CA was used to evapo-
rate the metal onto pristine SWNT surfaces under a pressure
lower than 1 106 torr. SWNT-metal contacts were formed
instantaneously without any further annealing treatment.
Then the samples were checked with a scanning electron
microscope SEM FEI XL30 from Philips to locate
SWNTs that were partially covered by the metal pads.
Atomic force microscope AFM Digital Instruments imag-
ing was performed to select desired SWNTs for study based
on their cleanness and diameter. Standard e-beam lithogra-
phy using polymethylmethacrylate PMMA as the resist and
lift-off process was then used to put a second electrode made
of 30 nm thick Au without a Ti or Cr adhesion layer onto the
uncovered part of the selected SWNTs to form an asymmet-
ric device structure, as shown in Fig. 1. The typical length
for SWNTs between metal electrodes was 3 m, and around
20 devices were fabricated for each type of contact before
ruling out metallic SWNTs. I-Vg measurements were per-
formed to rule out metallic SWNTs about 40%. Only semi-
conducting SWNTs are included in our discussion, and typi-
cal results are shown.
The choice of metal for electrodes is crucial for this
study. The reason is that to study the electronic characteris-
tics of metal-semiconductor junctions, other components in
the measurement circuit have to be orders of magnitude

0003-6951/2006/8813/133501/3/$23.00 88, 133501-1 2006 American Institute of Physics

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133501-2 Lu et al.
FIG. 1. a Color online SEM image of Al-SWNT-Au device; top elec-
trode is gold and bottom electrode is aluminum. b Schematic picture of
device structure.
lower in resistance. We chose Au without Cr or Ti adhesion
layer as the metal for the second electrode because it has
been shown experimentally that contact resistance between
noble metals and nanotubes can be very low, even reaching
the limit of Ohmic contact.4,11 We fabricated Au-SWNT-Au
devices to test the contact and found that such devices made
from semiconducting SWNTs had resistances taken with
10 mV drain voltage of less than 50 k at the on-state gate
voltage, 10 V and about 100 150 k at zero gating. Al-
though these values were far from the Ohmic contact limit,
they were no less than one order of magnitude lower than the
resistances measured from Ti-SWNT-Au and Al-SWNT-Au
devices under the same conditions. Therefore, we believe
that the data obtained from our devices reflect Ti- or Al-
SWNT contact properties.
Direct deposition of low work function metal through
shadow masks onto SWNTs was also a critical technique for
this work, since lift-off lithography leaves contamination on
SWNTs. Stable devices could only be made through direct
deposition of low work function metals, especially for Al.
In this study, SWNTs were exposed to air and holes were
the majority carriers. This p-type doping is thought to be due
to oxygen adsorption onto the SWNTs.19 According to semi-
conductor physics, a Schottky barrier forms at the contact
once low work function metals, such as Al and Ti, are
brought into contact with p-type SWNTs. TE and tunneling
are the two mechanisms for carrier transport through this
barrier, where the former is asymmetric and the latter is sym-
metric to the barrier.20,21 The TE current produces the recti-
fying behavior of a diode, but the symmetric tunneling cur-
rent is not desired. The barrier needs to be thick enough to
allow TE current only, and its thickness is related mostly to
the SWNT doping level, the metal work function, and the
SWNT electron affinity.21
Figure 2 shows I-V characteristics of an Al-SWNT-Au
device at different gate voltage conditions. This device
yielded an asymmetric rectifying I-V curve when Vg = 0 V,
which is characteristic for TE current.21 However, once the
SWNT barrier was negatively back gated electrostatically p
doped, tunneling current dominated the transport through
the barrier. As we can see in Fig. 2, at more negative gate
voltages, as the total current increased greatly, the I-V curve
became more and more symmetric. According to semicon-
ductor physics, in this p-type semiconductor and low work
function metal contact, when a more negative gate voltage is
added, Schottky barrier height decreases. Both TE current
and tunneling current increase when the barrier height low-
ers. However, the tunneling current is more sensitive to the
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Appl. Phys. Lett. 88, 133501 2006
FIG. 2. Color online I-V characteristics of AlAu contact at different gate
voltages. Al is grounded, bias applied on, and current measured from Au,
and Vg applied through back gate.
added gate voltage in that it is also related to the square root
of doping level of the semiconductor.21 That is because when
the SWNT was electrostatically p doped at more negative
gate voltages, the Schottky barrier thickness decreased
greatly. Consequently, tunneling current increases more rap-
idly and dominates the current through the barrier and the
I-V curves exhibit symmetric characteristics of the tunneling
process under large negative gate voltages. This phenomenon
was predicted by an earlier theoretical study22 but is not
readily observed in devices made from three-dimensional
semiconductors.
Ti-SWNT contact was also characterized, and its onset
Vg for rectifying I-V curves is more positive than that of Al
contact. As shown in Fig. 3, the I-V characteristic of Ti-
SWNT contact was symmetric when gate voltage was close
to zero 1 and +1 V. This indicates that either no barrier or
only a very thin barrier was formed at the contact, which
allowed tunneling current to pass through the contact readily.
When more positive gate voltages were applied, rectifying
I-V curves were obtained, indicating the emergence of a
thick Schottky barrier, quenching the symmetric tunneling
current. Another difference between Ti-SWNT contact and
Al-SWNT contact was that the total current through Ti-
SWNT contact was higher than through Al-SWNT contact at
the same drain voltage. Those differences indicate a much
thinner barrier in Ti-SWNT contact, which could not be ex-
plained by work function difference between Al and Ti, be-
cause Al has only a slightly lower work function 4.28 eV,
CRC Handbook of Chemistry and Physics than Ti 4.33 eV,
CRC Handbook of Chemistry and Physics.
We believe that chemical activity difference and surface
residues containing oxygen might be the major reasons for
those differences. In the gas phase, ionization energy de-
scribes the reactivity of one element. Al first ionization en-
FIG. 3. I-V characteristics of Ti-SWNT-Au device at different gate voltages.
Gate voltage is applied between back gate and ground, and Ti electrode is
also grounded. Current is measured from Au electrode.
133501-3 Lu et al.
FIG. 4. Color online I-V characteristics of three Al-SWNT-Au devices
with different SWNT diameters. Inset is the log scale plot.
ergy, 6.0 eV is much more reactive than Ti first ionization
energy, 6.8 eV. During metal evaporation, the Al atom is
more liable than Ti to react with water residue or dangling
hydroxide groups on the SiO2 surfaces where SWNTs reside.
Some interfacial aluminum oxide species are therefore
formed, thickening the barrier width to quench tunneling.
Titanium is less reactive in the gas phase, and less oxide is
formed during evaporation. So the Ti-SWNT barrier is thin-
ner than the Al-SWNT barrier, and the tunneling is more
significant. Larger positive gate voltages are then needed to
quench the tunneling current in Ti-SWNT contact.
During the process of writing this letter, we learned of
similar work by Manohara et al.,16 and their Ti-SWNT con-
tact did rectify at zero gate voltage. We noticed that their
device fabrication involved use of PMMA on SWNTs before
attaching Ti electrodes, and we think that a small amount of
PMMA residue could have helped to form the Schottky bar-
rier and thus yielded rectifying I-V curves in their study. This
is also compatible with the fact that the Schottky barrier is
very sensitive to semiconductor surface contamination.13
However, further investigation is needed to test this explana-
tion and further study on the effect of PMMA and other
residues on barrier formation is needed to gain better control
and understanding of Schottky barrier formation in this sys-
tem.
The relationship between Schottky barrier formation and
SWNT band structure is another interesting topic. There have
been reports on the diameter dependence of SWNT elec-
tronic properties.15,23 As stated previously, different metals
yield different barriers with similar SWNTs. Barrier forma-
tion between different SWNTs with the same metal could
further disclose the nature of the Schottky barrier at the
metal-SWNT junction. Figure 4 shows a comparison of I-V
curves of Al-SWNT junctions with SWNTs with different
diameters. For three devices made with different diameters,
the largest diameter device produced the highest forward cur-
rent under the same forward bias. This indicates that larger
diameter SWNTs formed lower Schottky barriers when
brought into contact with Al. The inset in Fig. 4 shows that
the log scale plot of the on-current is nearly a straight line at
low bias, which agrees with the description of Schottky bar-
rier forward current using the TE process.
In conclusion, we have fabricated Schottky barrier di-
odes with SWNTs by using asymmetric metal contacts. This
type of device allows us to explore metal-SWNT contact
properties directly. With well-established techniques from
studying three-dimensional 3D semiconductors,21 informa-
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Appl. Phys. Lett. 88, 133501 2006
tion about the Schottky barrier can be readily extracted. Car-
rier transports through different metal contacts were ex-
plored, and both the TE and tunneling processes were shown
to contribute to carrier transport through Schottky barriers.
Their competition, which can be tuned by gate voltages, was
shown both in Al-SWNT and Ti-SWNT contacts. The differ-
ence between Al-SWNT contact and Ti-SWNT contact was
large and unexpected, given that Al and Ti have similar work
functions. We propose that it is caused by the difference in
their capacity of forming thin oxide layers between metal
and SWNTs, because Al and Ti are very different in their first
ionization energies. Further work is needed for a better un-
derstanding of the Schottky barrier between metal electrodes
and SWNTs. This understanding is fundamentally important,
since metal-SWNT contact is unavoidable in SWNT elec-
tronic devices.
The project is in part supported by a grant from Northrop
Grumman and a Young Professor Award from DuPont. The
authors thank Professor Gleb Finkelstein and Alex
Makarovski in the Physics Department at Duke University
for helpful discussion and allowing us to use the facilities in
their laboratory.
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