APPLIED PHYSICS LETTERS 87, 073101 共2005兲

Photovoltaic effect in ideal carbon nanotube diodes

Ji Ung Leea兲
GE Global Research Center, Niskayuna, New York 12309
共Received 14 April 2005; accepted 29 June 2005; published online 8 August 2005兲
We demonstrate that individual single-walled carbon nanotubes 共SWNTs兲 can form ideal p-n
junction diodes. An ideal behavior is the theoretical limit of performance for any diode, a highly
sought after goal in all electronic materials development. We further elaborate on their properties by
examining photovoltaic effects, an application where its performance is intimately related to the
quality of the diode. Under illumination, SWNT diodes show significant power conversion
efficiencies owing to enhanced properties of an ideal diode. © 2005 American Institute of Physics.
关DOI: 10.1063/1.2010598兴

The p-n junction diode forms the basis for nearly all- Universally, all diode current-voltage 共I-V兲 characteris-
modern semiconductor electronics.1 As such, the quality of tics are compared to the diode equation1
the diode is often a good predictor of the performance of a
semiconductor device. A diode is degraded by impurities and IDS = Io共eqVDS/nkBT − 1兲, 共1兲
structural defects in the semiconductor, forming defect states
in the energy band gap. Commensurate with defect states are where Io is the saturation current, q is the electronic charge,
deviations from the theoretical ideal behavior of a diode.1 VDS is the voltage across the junction, n is the ideality factor,
Nowhere is the quality and performance relation more inti- kB is Boltzman’s constant, T is the absolute temperature. n is
mate than in the photovoltaic 共PV兲 application.1–4 This is precisely equal to 1 for an ideal diode but approaches 2 for
because two charge carriers, electrons and holes, are created materials with defects. The ideality factor is intimately re-
when photons of sufficient energy are absorbed in a semicon- lated to the performance of a PV diode. The larger the n, the
ductor. Together, they probe a wider range of defect energy lower the power conversion efficiency through reduced
levels through recombination than a unipolar device involv- open-circuit voltage as described below.2,4
Previously, we reported on a new method to form p-n
ing only one of the carriers. Here, we demonstrate that indi-
junction diodes along a single SWNT using electrostatic
vidual single-walled carbon nanotubes 共SWNTs兲 can form
doping15 but with nonideal behavior. The principle of elec-
ideal p-n junction diodes, providing direct evidence for their
trostatic doping was demonstrated using a device structure
structural purity. We further elaborate on the ideal behavior
similar to that shown in the inset of Fig. 1, but with SWNTs
by examining PV effects, an application where the conver-
resting completely on SiO2. Different bias polarities on the
sion efficiency of photon energy to electrical power is di-
rectly related to the quality of the diode.1–4
Additionally, SWNTs may provide unique advantages
for PV. They offer a wide range of band gaps5 to match the
solar spectrum, enhanced optical absorption,6,7 and reduced
carrier scattering for hot carrier transport.8,9
A necessary component in a PV device is a built-in elec-
tric field that separates the photogenerated electron-hole
共e-h兲 pairs. Early bulk semiconductor devices utilized metal/
semiconductor Schottky diodes where the difference in the
work function between these two materials resulted in the
built-in electric field.3 However, these make inefficient PV
devices because the full band-gap of the semiconductor is
never utilized, resulting in poor device performance from
reduced photovoltage and high leakage currents. The p-n
junction diode overcomes these issues and serves as the
model system with the highest-power conversion
efficiencies.3,4 Previous results dealing with photocurrents in
SWNTs were either Schottky or ohmic contacted
devices,10–12 or possibly thermoelectric devices13 with no de-
tails on the relation between photogenerated current and
voltage. PV devices utilizing small amounts of SWNTs in a
conjugated polymer blend have been reported with poor
efficiencies.14 Here, we examine the fundamental properties FIG. 1. 共Color兲 The inset shows the split gate device where VG1 and VG2
of nanotubes by examining individual ideal SWNT diodes. are biased with opposite polarities 共VG1 = −VG2 = + 10 V兲 to form an ideal
p-n junction diode along a SWNT. Data are typical dark current-voltage
共I-V兲 curve at T = 300 K with a fit to Eq. 共1兲 using I0 = 8.0⫻ 10−13 A, n
a兲
Electronic mail: leeji@research.ge.com = 1.0 with a series resistance Rs = 18⫻ 106 ohms.

0003-6951/2005/87共7兲/073101/3/$22.50 87, 073101-1 © 2005 American Institute of Physics

073101-2 Ji Ung Lee Appl. Phys. Lett. 87, 073101 共2005兲

split gate electrostatically couple to form separate regions of

electron and hole doping along a single SWNT. This is pos-
sible because the metal contacts make Schottky barriers,16
allowing either electrons or holes to tunnel into the nanotube.
These diodes exhibited good rectification with n between 1.2
and 1.3. Conversely, when SWNTs are suspended as shown
in the inset of Fig. 1, the diodes become ideal. We, therefore,
postulate that defect-free SWNTs interact with the surface on
which they rest, creating states in their band gap leading to a
nonideal behavior.
The fabrication process followed standard lithography
and etch techniques, and SWNTs were grown using catalytic
chemical vapor deposition techniques.17 Briefly, a 400 nm
thermal oxide was grown on a heavily doped Si wafer. Using
standard lithography and deposition techniques, split gates
were formed using Mo, with gate spacing ranging from
0.5 ␮m to 1 ␮m. Using the split gate metal as an etch mask,
250 nm of oxide was dry etched. This process left vertical
sidewalls with minimal gate metal damage and roughness.
Next, 150 nm of oxide was deposited, forming the gate di- FIG. 2. 共Color兲 I-V characteristics under increased light intensity showing a
electric for the split gate. The S and D contacts were then progressive shift into the fourth quadrant 共PV兲 where the diode generates
power. The inset shows the expected linear increase in the current measured
lithographically defined. Finally, SWNTs were grown on top
at VDS = 0 共Isc兲 with illuminated power.
of the S and D metals. A large number of devices are fabri-
cated and many are found with only a single semiconducting
SWNT between S and D as observed in a scanning electron tons. Therefore, injection from the metal contacts is not sig-
microscope. Figure 1 shows a typical I-V curve with the split nificant.
gate biased in a diode configuration 共VG1 = −VG2 = + 10 V兲 The key metric for a PV diode is the efficiency in which
along with a fit to Eq. 共1兲 that includes a series resistance light energy is converted to electrical power. Figure 3共b兲 il-
contribution from the contacts to fit the roll-off above lustrates several important performance figures of merit us-
10−9 A. The fit is with n = 1.0, the ideality factor of an ideal ing the SWNT diode. In addition to ISC and VOC, two addi-
diode.
To examine the I-V characteristics under illumination,
we used a 1.5 ␮m 共0.8 eV兲 continuous wave laser diode
共ANDO, AQ8203兲 with a variable output power up to
10 mW. Since the photon energy is below the band gap of
the underlying Si substrate, no electrostatic response from Si
is expected under illumination. The infrared 共IR兲 light is
coupled to a multimode fiber and positioned 100– 200 ␮m
from the devices. The light exiting the fiber is circularly
polarized. The power density was approximated by the
power delivered from the laser and the area of the fiber core.
Figure 2 shows the dark I-V characteristics with those under
increased illumination intensity as indicated by the arrow.
The region of power generation is marked PV. The inset
shows the expected linear dependence of the measured pho-
tocurrent at zero voltage bias 共ISC兲 with IR power density.
The energy band diagram in Fig. 3共a兲 summarizes the
essential physics of operation of SWNT PV diodes. The
doped regions are depicted with capacitive coupling to the
split gate electrodes. In the middle of the device, where the
built-in field is greatest, photogenerated e-h pairs become
separated, causing currents to flow. Under a forward bias,
flow of carriers from the doped ends is opposite the flow
from the photogenerated carriers. At VDS = VOC, these two
currents cancel and result in a zero net current. We also note
that ISC showed either no dependence or a small increase
with increased doping 共increased 兩VG1,2兩兲, consistent with
band-to-band generation of e-h pairs. On the other hand, in- FIG. 3. 共Color兲 共a兲 The energy band diagram of an electrostatically doped
jection of carriers from metal contacts by photoexcited car- SWNT diode showing currents from photogenerated e-h pairs and the for-
ward biased currents. 共b兲 The fourth quadrant I-V curve and power
riers should show a strong dependence on the barrier 共Power= IDS ⫻ VDS兲 showing several important figures of merit: Isc and Voc
height,18 which we have varied by 0.3 eV or more by vary- describe the characteristics under illumination, while I M and V M describe the
ing VG1,2, a significant fraction of the 0.8 eV energy pho- bias point where the power generation is at a maximum.
073101-3 Ji Ung Lee
FIG. 4. 共Color兲 Measured values of the open circuit voltage Voc vs Isc / Io at
T = 300 K 共Io is the reverse biased saturation current兲. The inset shows the
measured Io, covering roughly every decade change in Io.
tional parameters, VM and I M , describe the potential
usefulness of a diode. They mark the bias point where the
power generation 共P = IDS ⫻ VDS兲 is at a maximum. Together,
ISC, Im, VOC, and V M define the fill factor 共FF兲3,4 of a PV
diode as FF= I M V M / ISCVOC. It is a measure of the “square-
ness” of an I-V curve, or simply a measure of the available
power. FF will always be less than 1 due to the rounded
features of an exponential I-V curve and is larger for larger
VOC.4 For our devices, FF ranged from 0.33–0.52 and is con-
sistent with the measured values of VOC. To examine the
parameters that govern VOC, we express the I-V characteris-
tics under illumination as3,4
IDS = − ISC + Io共eqVDS/kBT − 1兲. 共2兲
For IDS = 0, we obtain:
冋 册
k BT ISC
VOC = ln +1 . 共3兲
q Io
Equation 共3兲 is simply the ideal diode equation expressed in
terms of the new diode parameters under illumination and
represents the highest VOC achievable for any diode.4 For
SWNTs, a wide range of ISC / Io can be examined due to
different band-gap semiconductors with varying saturation
currents, Io. By also varying the illumination intensity, ISC / Io
was examined from 0.1⬍ ISC / Io ⬍ 104. Figure 4 shows a plot
of measured VOC for several diodes as a function of ISC / Io,
along with Eq. 共3兲. The inset shows the measured Io. For an
ideal diode Io ⬃ e−qEG/kBT, where EG is the band gap1,2 and,
therefore, a measure of the activation energy. Based on the
activation energy of the examined diodes 共data not shown兲,
the Io shown in the inset corresponds to EG in the rage of
0.6– 0.8 eV.17 Based on these energies, the incident light ex-
cites the first subbands of SWNTs suggesting strong quasi-
particle excited state in nanotubes. ISC measured at the maxi-
mum intensity 共highest VOC in each data set兲 ranged from
2 – 5 pA. It can be seen that the maximum VOC increases with
decreasing Io as expected. The excellent agreement with Eq.
Appl. Phys. Lett. 87, 073101 共2005兲
共3兲 highlights the potential of SWNTs in PV applications as
summarized below.
The power conversion efficiency ␩ can be estimated
from the short-circuit current density Jsc calculated from the
illuminated area of a SWNT. The typical responsivity was
Jsc / Pin = 30 mA/ W, where Pin is the incident power density.
We find that ␩ = 共Jsc / Pin兲 ⫻ Voc ⫻ FF is the highest for devices
with the lowest Io, because of higher VOC and FF. The maxi-
mum value of ␩ was 0.2%. This is significant considering
only a small fraction of the incident power is absorbed. The
small diameter of SWNTs and the circularly polarized light
contribute to the small absorption. A reasonable estimate
based on the actual absorbed power suggests ␩ ⬎ 5%.10,19,20
A significant improvement in ␩ can be expected by consid-
ering a 0.8 nm diameter SWNT with a band gap of 1.4 eV,21
the ideal band gap of a single bulk junction device at the
standard solar spectrum.4 For the same responsivity, based
on the reduction in the leakage current by at least 1010 com-
pared to a 0.8 eV band-gap SWNT, extrapolated Voc
⬎ 0.8 V and FF⬎ 0.8 are calculated, values comparable or
higher than bulk PV diodes.3 Further improvements in ␩ can
be expected when considering a network of tubes where
strong electromagnetic coupling and scattering between
nanotubes22,23 could lead to higher responsivity.
J. U. L. would like to thank J. Balch, J. Galea, P. Gipp,
A. Johnson, J. Kretchmer, M. Lazzeri, P. Mowers, and R.
Whitney for device fabrication and mask layout. Support
from M. L. Blohm and the Nanotechnology Program at GE
Global Research Center are appreciated.
1
S. M. Sze, Physics of Semiconductor Devices 共Wiley, New York, 1981兲.
2
W. Shockley and H. J. Queisser, J. Appl. Phys. 51, 510 共1961兲.
3
J. Nelson, The Physics of Solar Cells 共Imperial College, London, 2003兲.
4
M. A. Green, Solar Cells: Operating Principles, Technology, and Appli-
cations 共Prentice–Hall, Englewood Cliffs, NJ, 1982兲.
5
R. Saito, G. Dresselhaus, and M. S. Dresselhaus, Physical Properties of
Carbon Nanotubes 共Imperial College, London, 1998兲.
6
J. W. G. Wilder, L. C. Venema, A. G. Rinzler, R. E. Smalley, and C.
Dekker, Nature 共London兲 391, 59 共1998兲.
7
T. W. O. Odom, J. L. Huang, P. Kim, and C. M. Lieber, Nature 共London兲
391, 62 共1998兲.
8
M. Freitag, V. Perebeinos, J. Chen, A. Stein, J. C. Tsang, J. A. Misewich,
R. Martel, and P. Avouris, Nano Lett. 4, 1063 共2004兲.
9
J. Guo, C. Yang, Z. M. Li, M. Bai, H. J. Liu, G. D. Li, E. G. Wang, C. T.
Chan, Z. K. Tang, W. K. Ge, and X. Xiao, Phys. Rev. Lett. 93, 017402
共2004兲.
10
M. Freitag, Y. Martin, J. A. Misewich, R. Martel, and P. Avouris, Nano
Lett. 3, 1067 共2003兲.
11
K. Balasubramanian, Y. Fan, M. Burghard, K. Kern, M. Friedrich, U.
Wannek, and A. Mews, Appl. Phys. Lett. 84, 2400 共2004兲.
12
Y. Ohno, S. Kishimoto, T. Mizutani, T. Okazaki, and H. Shinohara, Appl.
Phys. Lett. 84, 1368 共2004兲.
13
Y. Zhang and S. Iijima, Phys. Rev. Lett. 82, 3472 共1999兲.
14
E. Kymakis and G. A. J. Amaratunga, Appl. Phys. Lett. 80, 112 共2002兲.
15
J. U. Lee, P. P. Gipp, and C. M. Heller, Appl. Phys. Lett. 85, 145 共2004兲.
16
S. Heinze, J. Tersoff, R. Martel, V. Derycke, J. Appenzeller, and P.
Avouris, Phys. Rev. Lett. 89, 106801 共2002兲.
17
J. Kong, H. T. Soh, A. M. Cassell, C. F. Quate, and H. Dai, Nature
共London兲 395, 878 共1998兲.
18
R. H. Fowler, Phys. Rev. 38, 45 共1931兲.
19
G. Y. Guo, K. C. Chu, D. Wang, and C. Duan, Phys. Rev. B 69, 205416
共2004兲.
20
D. A. Stewart and F. Leonard, Nano Lett. 5, 219 共2005兲.
21
S. M. Bachilo, M. Strano, C. Kittrell, R. H. Hauge, R. E. Smalley, and R.
B. Weisman, Science 298, 2361 共2002兲.
22
M. Y. Sfeir, F. Wang, L. Huang, C. C. Chuang, J. Hone, S. P. O’Brien, T.
F. Heinze, and L. E. Brus, Science 306, 1540 共2004兲.
23
F. J. Garica-Vidal, J. M. Pitarke, and J. B. Pendry, Phys. Rev. Lett. 78,
4289 共1997兲.