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IEEE TRANSACTIONS ON MICROWAVE THEORY AND TECHNIQUES, VOL. 59, NO. 10, OCTOBER 2011
Single Carbon Nanotube Schottky Diode
Microwave Rectifiers
Enrique D. Cobas, Steven M. Anlage, Member, IEEE, and Michael S. Fuhrer
Abstract—We report the fabrication of single and few-channel
carbon nanotube (CNT) Schottky diodes on high-frequency
compatible substrates using horizontally aligned CNT arrays
and dissimilar metal contacts in a coplanar-waveguide geometry.
Rectification of ac signals in the range of 100 MHz–40 GHz is
examined and the observed cutoff frequencies are used to compute
the Schottky junction capacitance of the devices, which is strongly
CNT-length-dependent and appears dominated by stray capacitance between the CNT channel and metal electrode, in agreement
with electrostatic simulations.
Index Terms—Carbon nanotubes (CNTs), impedance mismatch,
microwave rectification, Schottky diodes.
I. INTRODUCTION
HE high-frequency properties of carbon nanotubes
(CNTs) have been of interest to the academic community
for some time due to their useful bandgap [1], [2], high sustainable transport current density [3], high carrier mobility [4], long
mean-free path [5], [6], and small capacitances, all properties
they exhibit at room temperature. In addition, these 1-D systems challenge some assumptions about device electrostatics
and charge transport. Significant quantum capacitance and
kinetic inductance[7] introduce novel device physics. Further,
electron–electron interactions are inevitable in one dimension,
the charge carriers cannot be described as electron-like (Fermi
liquid), but instead are plasmon-like (Luttinger liquid [8]–[12])
and transport charge at a velocity that is significantly different
than the Fermi velocity. These properties and novel phenomena
point to the possibility of terahertz CNT devices, including
transistors, amplifiers [13], and oscillators [14], [15].
Reviews of the theoretical expectations for the high-frequency properties of these nanostructures have been performed
by Burke [16] and others [17]. One of the principal obstacles
to the use of CNTs in high-frequency electronics is their high
T
Manuscript received March 03, 2011; revised June 29, 2011; accepted July
08, 2011. Date of publication September 15, 2011; date of current version October 12, 2011. This work was supported in part by the U.S. Office of Naval
Research through the Center for Applied Electromagnetics, University of Maryland at College Park.
E. D. Cobas was with the Department of Physics and the Center of
Nanophysics and Advanced Materials, University of Maryland at College Park, College Park, MD 20742 USA. He is now with the U.S. Naval
Research Laboratory (NRL), Washington, DC 20375 USA (e-mail:
[email protected]).
S. M. Anlage and M. S. Fuhrer are with the Department of Physics and
the Center for Nanophysics and Advanced Materials, University of Maryland
at College Park, College Park, MD 20742 USA (e-mail:
[email protected];
[email protected]).
Color versions of one or more of the figures in this paper are available online
at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/TMTT.2011.2164548
individual impedance. The quantum of conductance for a single
quantum channel can be calculated by integrating the density
of states between source and drain potentials
(1)
where
and
are the source and drain potentials,
and
are the momenta of the states at energies of
and , and
is the source–drain voltage. Thus, the conductance of a
independent of any matequantum channel is limited to
rials parameters, even without scattering. Spin and band degeneracy in CNTs produce a total of four parallel quantum chank for
nels, yielding a minimum impedance of
a single CNT. The impedance mismatch with traditional 50equipment produces signal transmission factors below 10 . To
avoid this problem, devices can be based on a large number of
parallel CNT channels that provide a better match to the 50standard. Although obstacles remain in the control or sorting of
nanotube types, this approach has produced promising results,
including device cutoff frequencies up to 23 GHz [18] and intrinsic cutoff frequencies up to 80 GHz [19] in field-effect transistor (FET) geometries. However, using many parallel CNTs,
especially of different types, may blur and obscure phenomena
unique to these 1-D systems.
To characterize few-CNT systems at microwave frequencies,
we must deal with the high-impedance mismatch between
them and the macroscopic world. One approach proposed by
Manohara et al. [20] is the creation of Schottky diodes using
semiconducting CNTs (CNT-SDs). Manohara et al. fabricated
diodes on SiO Si, which was unsuitable for high-frequency
characterization. In a previous study, we improved upon this
approach by fabricating CNT Schottky diodes on quartz substrates using a patterned catalyst approach, and demonstrated
rectification of microwave signals up to 18 GHz introduced in
the far field and coupled somewhat uncontrollably to the device
[21].
In this study, we improve upon our previous work by creating
CNT-SDs from arrays of aligned CNTs prepared on quartz substrates with coplanar-waveguide (CPW) contacts. This arrangement enables us to probe electrical transport in CNTs as a function of frequency (up to our equipment limit of 40 GHz) with
a good signal-to-noise ratio (SNR). The maximum operating
, is determined by the
frequency of these rectifiers,
channel resistance and junction capacitance. The latter is exF range [10], [22]–[25] and in parallel
pected to be in the 10
with a larger parasitic capacitance, making it difficult to measure
experimentally. Here we use the high-frequency cutoff values
0018-9480/$26.00 © 2011 IEEE
COBAS et al.: SINGLE CNT SCHOTTKY DIODE MICROWAVE RECTIFIERS
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Fig. 2. Conventional circuit model for a Schottky diode shown in parallel with
a parasitic capacitance C .
Fig. 1. (left) SEM image of the CPW electrode geometry and (right) close-up
of the active device area. The center electrode (bottom feature on the close-up)
is the Schottky contact, while the outer electrode (top in the close-up) is ohmic.
(2)
observed to extract the junction capacitance
of bias, channel length, and ambient doping.
, as a function
II. DEVICE FABRICATION
Horizontally aligned arrays of CNTs were synthesized via
chemical vapor deposition (CVD) using ferritin catalyst on
st-cut quartz substrates following the approach of Kocabas et
al. [26]. A further detailed review of synthesis parameters was
performed by Routstka et al. [27]. Conventional photolithography was used to pattern an array of 50- CPW electrodes.
Angled evaporation of chromium–gold (chromium work function 4.5 V) and platinum contacts (work function 5.6 V) was
exploited to produce asymmetric contacts to the CNTs (work
function 4.8 eV [28], [29]), as in our previous study [21]. Due
to oxygen and moisture [30], the CNTs are doped p-type in
ambient conditions, making holes the majority carrier type and
creating a p-type Schottky barrier at the chromium contact. The
resulting Schottky diodes (CNT-SDs) are similar to those of
Manohara et al. [20]. A second photolithography step, followed
by oxygen plasma etching, removed all the CNTs outside of
the target device area. One of the devices is shown in Fig. 1.
The close-up shows several nanotubes that extended beyond
the device area and were cut by plasma etching. Contrast
differences between nanotubes are due to a voltage-contrast
mechanism [31] such that only nanotubes connected to the
metal leads appear bright.
III. DC MEASUREMENTS
DC characterization of the 100-device array showed a diode
yield under 5%, with other devices exhibiting either: 1) constant bias-independent background conductivity; 2) very high
impedance; or 3) open-circuit impedance. These conditions are
consistent with: 1) a metallic nanotube in the channel; 2) very
high contact resistance; and 3) the absence of a contacted CNT
in the device area, respectively.
Fig. 2 shows the conventional circuit model for a Schottky
diode [2], in parallel with a purely reactive parasitic capacitance
. Here,
represents the series resistance of the diode circuit, in this case, the combined resistance of the CNT channel
and contacts under forward bias
is the bias-dependent
resistance of the Schottky junction and
is the capacitance
is determined
across the Schottky barrier. We expect that
by the Shockley diode equation
where
is the junction voltage. It is clear that the voltage seen
by the diode is equal to that applied to the parasitic capacitance.
Further, rectification occurs only due to the variable junction
, which is expected to have an exponential deresistance
pendence on applied bias. Measurements at dc exhibit this exponential dependence at low bias, followed by a linear
characteristic at high bias, consistent with
having fallen
to a negligible value, compared to a linear . We can extract
both resistances from the dc – measurements.
Using the
and
values extracted from the – characteristic, we calculate the fraction of applied voltage that is
present as a potential drop across the Schottky junction . In
Fig. 3, we plot the current flowing across the junction as a funcand fit the resulting data to the Shockley diode (1)
tion of
for two of our CNT-SDs. The ideality factors calculated from
the fits vary widely, between 2–20, indicating that although the
,
current follows the expected exponential dependence on
the mechanisms of current transport may not be the traditional
thermionic emission and diffusion that limit the ideality factor
to 2. Tunneling may play a significant role in these 1-D sysought to
tems [32]. The value of the junction capacitance
depend on the depletion region width. The problem of charge
carrier density in a 1-D pn-junction was explored by Leonard
and Tersoff [33] and Krowne [34]. Findings indicate that lack
of shielding in a 1-D semiconductor leads to significantly extended charge carrier density profile. This density also depends
on doping fraction, with the dominant doping in ambient CNT
systems arising from oxygen and moisture [30], [35].
IV. HIGH FREQUENCY MEASUREMENTS
At high frequencies, the impedance of the parasitic capacand that of the measurement circuit
itance
(50 ) will determine the voltage at the CNT device terminals.
The parasitic capacitance for these devices is the CPW open-circuit capacitance
, estimated by [36]
(3)
(4)
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IEEE TRANSACTIONS ON MICROWAVE THEORY AND TECHNIQUES, VOL. 59, NO. 10, OCTOBER 2011
Fig. 5. Rectified current (in units of nanoamps per milliwatt) for a CNT-SD as
a function of ac frequency and dc offset bias.
Fig. 3. Measured I –V characteristics of two CNT-SDs (black dots) with superimposed fits (red solid lines in online version) to the Shockley diode equation
(1).
Fig. 4. Circuit diagram for the measurement setup showing the diode (DUT)
connected to a bias tee (capacitor and inductor), microwave source (V ), dc
source (V ), and a lock-in amplifier.
where
and
,
is the effective
dielectric constant for the CPW, and
the permittivity of a
m is the inner electrode
vacuum. For our devices,
m is the lateral separation between inner and
width,
outer CPW electrodes, and the channel length varied between
0.5–25 m. The value of
is in the range of 1 fF such that
the parasitic capacitance becomes comparable to a short circuit
only at frequencies above 3 THz and can thus be ignored in
the frequency range studied here. This capacitance value is in
agreement with the result of numerical simulations of our CPW
geometry performed in Ansoft Maxwell 3D.
High-frequency measurements were performed at room temperature in a probe station using 50- air coplanar (ACP) microwave probes. The measurement circuit is described in Fig. 4.
The CNT-SD was connected, via the microwave probe, to a
broadband (50 GHz) bias tee. The ac branch was connected
Fig. 6. (a) Calculated bias-dependent cutoff frequency f (V ) assuming various trial junction capacitance values [1 aF (in red in online version), 10 aF (in
green in online version), 100 aF (in blue in online version)] and the observed
cutoff frequencies (black circles) for a 20-m-long device. (b) Experimentally
determined junction capacitance as a function of frequency (red circles in online
version), extracted from the observed cutoff frequency using (5). Green line (in
online version) shows the mean value of the junction capacitance of 108 aF.
to a 40-GHz signal generator
, amplitude modulated at
Hz. The rectified current (in the dc branch) was
measured with a lock-in amplifier, which had ground-isolation
in the diagram). An offset
impedance of 10 k (labeled
COBAS et al.: SINGLE CNT SCHOTTKY DIODE MICROWAVE RECTIFIERS
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Fig. 7. Capacitance per nanotube channel as a function of device length; data
are also in Table I. The vacuum values are slightly offset for clarity. Inset: Loglinear scale.
TABLE I
CHANNEL LENGTH l , SERIES RESISTANCE R , DIODE IDEALITY FACTOR n,
NUMBER OF NANOTUBES N , AND EXTRACTED JUNCTION CAPACITANCE
C UNDER AMBIENT AND VACUUM CONDITIONS
voltage
was applied to the CNT-SD via the low input of
the amplifier.
This setup enabled control of microwave frequency and amplitude, as well as offset dc voltage. Parameter ranges studied
MHz
GHz, power
dBm
included
dBm (0.01–32 mW) and
V
V. The only
calibration performed was a power-flatness calibration of the
microwave source. This was done by replacing the ACP probe
with a custom adapter, connected to a broadband microwave
power sensor (HP 8457C). The power calibration therefore replaces the loss properties of the ACP probe with those of the
simple cable adapter. The rectified current measured is therefore shown in units of amps per milliwatt of applied signal,
i.e., the detectivity. Fig. 5 shows the measured detectivity of the
CNT diodes as a function of frequency of the applied signal,
and as a function of dc bias on the CNT. Fig. 5 shows an expected bias-dependent roll-off of detectivity in frequency. For
the model circuit of Fig. 2, the bias-dependent cutoff frequency
for a Schottky diode is given by [2]
(5)
Fig. 8. Extracted junction capacitance in vacuum as a function of dc bias for
CNT-SDs with channel lengths of: (a) 1 m, (b) 3 m, and (c) 7 m.
where the other terms have the same meanings as described
above. The variation of the cutoff frequency with applied bias
is shown in Fig. 6. As forward bias increases, the junction refalls exponentially, and the combined
time
sistance
constant of the device rises to higher frequencies (in this case,
from 950 MHz to 3.6 GHz for the biases shown). The measurement was repeated in ambient and vacuum 10 torr conditions to explore the effect that oxygen and ambient moisture
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IEEE TRANSACTIONS ON MICROWAVE THEORY AND TECHNIQUES, VOL. 59, NO. 10, OCTOBER 2011
Fig. 10. Results of capacitance calculated from 3-D numerical simulations,
showing a much stronger dependence on channel length than depletion length.
Fig. 9. 3-D model used for numerical capacitance calculations. (a) Overall
view of the conducting cylinder and rectangular electrode on a quartz substrate
and (b) close-up view of the gap between the channel and electrode, which represents the depletion region.
doping [30] might have on the charge carrier density and the
depletion region width.
V. ANALYSIS: JUNCTION CAPACITANCE
VERSUS CHANNEL LENGTH
The solid lines in Fig. 6(a) show the predictions of 5 for
for several different values of the junction capacitance
, superimposed on the observed cutoff frequency values (circles) for
a single-CNT 20- m-long CNT-SD. There is good agreement
for bias values explored, from 0 to 1.25 V, corresponding to
cutoff frequencies between 300 MHz–9 GHz, and a constant capacitance value of 108 aF. This result is shown more explicitly
in Fig. 6(b), where the capacitance was extracted from the observed cutoff frequency and (4). The same measurements were
performed on CNT diodes comprised of three parallel CNTs
each with channel lengths of 7, 3, and 1 m. The extracted junction capacitance values for these shorter devices were all under
20 aF despite having three parallel junctions each. As shown
in Fig. 7, the capacitance per junction is found to be strongly
related to channel length, suggesting that stray capacitance between a long CNT channel and a metal electrode dominates
junction capacitance in long-channel devices.
In order to explore the effect of doping, the devices were also
measured under vacuum conditions 10 torr . Fig. 8 shows
the junction capacitance, extracted from the observed cutoff fre] for a
quencies, as a function of junction voltage [i.e.,
CNT-SDs of 1-, 3-, and 7- m channel lengths. A positive relation between capacitance and dc bias is observed.
VI. NUMERICAL SIMULATION
Numerical simulations were used to explore the relationship
between channel length, depletion length, and junction capacitance. The system was modeled in Ansoft Maxwell 3-D v12 as
a conducting cylinder and rectangular electrode separated by a
variable gap , representing the depletion region width, laying
on top of a quartz substrate, as shown in Fig. 9. A parametric
analysis was performed to vary the critical system dimensions
(e.g., depletion length, tube length, etc.) and the capacitance was
calculated for each solution. The calculated dependencies of
junction capacitance to depletion length and nanotube channel
length are shown in Fig. 10(a) and (b). Fig. 10(a) shows that
capacitance is relatively insensitive to variations in depletion
width, while Fig. 10(b) shows that capacitance depends strongly
on the CNT length. This indicates that, for the parameters explored here, the capacitance is dominated by stray capacitance
COBAS et al.: SINGLE CNT SCHOTTKY DIODE MICROWAVE RECTIFIERS
2731
occurs is seen to scale with electrode width. These results support our hypothesis that stray capacitance dominates junction
capacitance in long-channel devices.
The junction voltage-dependent capacitances in vacuum
(Fig. 8) do show a slight increasing dependence of capacitance
on junction voltage, as expected for narrowing of the depletion
width with voltage. The observation of this effect in devices
in vacuum likely indicates that doping by ambient species
reduces the depletion width to small values in ambient [35],
and removal of doping in vacuum allows the depletion width to
be modulated more significantly by bias voltage.
VII. HIGH-FREQUENCY TRANSPORT
Fig. 11. Calculated capacitance values for various channel lengths as a function
of electrode width.
Finally, the rectified signal was used to probe transport up
the equipment limit of 40 GHz. Fig. 12 shows two examples of
very high-frequency rectification. The large peaks in the rectified signal with periodicity of 3 GHz correspond to resonances
in the microwave probe assembly that were not calibrated out by
the power flatness calibration. Nevertheless, two important facts
can be gleaned from the data. Fig. 12(a) shows a minimum in the
rectified signal at 1.0- and 1.1-V dc bias and 25 GHz, followed by a recovery of rectification at higher frequencies. This
phenomenon is not understood, but serves as an example of the
utility of this technique in examining unusual phenomena in RF
1-D transport. Fig. 12(b) shows data from a CNT-SD at frequencies up to 40 GHz. The bias dependence reveals a noise floor of
0.2 nA and a maximum signal of 100 nA at 40 GHz, yielding an
SNR of 500:1.
VIII. CONCLUSION
Fig. 12. Rectified current signal from a CNT-SD showing: (a) bias-dependent
minima in the rectified signal at 26 GHz and (b) bias-dependent SNR of 500 at
40 GHz.
of the CNT length to the electrode. Fig. 10(b) also shows that
the capacitance saturates for long CNT lengths. This is further
explored in Fig. 11, where calculations were performed with
different electrode widths. The CNT length at which saturation
We have demonstrated the use of Schottky rectification as a
probe of high-frequency electrical transport in high-impedance
semiconducting nanosystems. We expect this technique will be
particularly useful for 1-D systems (semiconducting CNTs and
small semiconducting nanowires) because these systems exhibit
quantized conductance and cannot be impedance matched to
macroscopic RF equipment. We have used this technique to examine the capacitance of CNT Schottky barriers as a function
of bias and ambient pressure and doping. We find that the capacitance of long-channel CNT-SDs is dominated by stray capacitance between the metal electrode and the bulk of the nanotube channel and exhibits no dependence on dc bias, in agreement with numerical simulations. For short-nanotube diodes
with doping reduced in vacuum, we find junction capacitance
values under 10 aF, which exhibit a positive relation with forward bias, consistent with the hypothesis of increasing Schottky
barrier capacitance as the length of the depletion region decreases.
We expect that these measurements could be significantly
improved by calibrating the power reaching the device. By
using a 50- load fabricated in a CPW geometry on a quartz
substrate, it would be possible to calibrate out the microwave
probe assembly’s transmission resonances and get a clearer
picture of the frequency response of the CNT-SD devices out
to 40 GHz or beyond. Furthermore, improvement of the series
resistance should be possible by doping, cleaner fabrication
methods, and by annealing the contact. Such improvements,
combined with the Schottky barrier capacitances of 10 aF, point
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IEEE TRANSACTIONS ON MICROWAVE THEORY AND TECHNIQUES, VOL. 59, NO. 10, OCTOBER 2011
to the possibility of single-tube CNT-SDs with bandwidths
exceeding 100 GHz. Low-temperature measurements would
also clarify the transport mechanism at the barrier while simultaneously providing a longer mean-free path to enable detection
of Fermi or Luttinger liquid plasmon velocity resonances.
With stray capacitances of order 10 aF or greater and junction resistance necessarily larger than 6 k , it is unlikely that the
cutoff frequency of a single-nanotube device will exceed 1 THz.
However, the stray capacitance will scale sub-linearly with the
number of tubes, while the junction resistance and series resistance should scale inversely with tube number. Thus, bundles
or parallel arrays of CNTs [18], [19] could show an even higher
cutoff frequency.
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Enrique D. Cobas, photograph and biography not available at time of publication.
Steven M. Anlage (A’95–M’08), photograph and biography not available at
time of publication.
Michael S. Fuhrer, photograph and biography not available at time of publication.