Carbon nanotube arrays based

high-performance infrared
photodetector [Invited]
Qingsheng Zeng,1 Sheng Wang,1,5 Leijing Yang,1,2 Zhenxing Wang,1 Tian Pei,1
Zhiyong Zhang,1 Lian-Mao Peng,1,6 Weiwei Zhou,3 Jie Liu,3 Weiya Zhou,4
and Sishen Xie4,7
1
Key Laboratory for the Physics and Chemistry of Nanodevices, Department of Electronics, Peking University,
Beijing 100871, China
2
Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China
3
Department of Chemistry, Duke University, Durham, North Carolina 27708, USA
4
Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
5
shengwang@pku.edu.cn
6
lmpeng@pku.edu.cn
7
ssxie@iphy.ac.cn

Abstract: The carbon nanotubes (CNTs) are an ideal material for infrared
applications due to its excellent electronic and optoelectronic properties,
suitable bandgap, mechanical and chemical stabilities. In this paper, we
demonstrate a photovoltaic infrared detector which is based on aligned
single-walled CNT (SWCNT) arrays. The device is fabricated by
asymmetrically contacting the two ends of the SWCNT arrays with Pd and
Sc of different work functions, which are known to form ohmic contacts
with the valence and conduction bands of semiconducting SWCNTs
respectively. The device is characterized at room temperature, exhibiting
excellent diode characteristics, high responsivity of 9.87 × 10−5 A/W and
infrared spectral detectivity of 1.09 × 107 cmHz1/2/W. The demonstration of
the SWCNT arrays based infrared detector which is fabricated using a
doping-free process paves the way to applications of CNT in such field as
high-performance infrared sensors.
©2012 Optical Society of America
OCIS codes: (040.3060) Infrared; (040.5160) Photodetectors; (040.5350) Photovoltaic;
(160.4236) Nanomaterials; (230.5170) Photodiodes.

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1. Introduction
Infrared (IR) detection is a primary subject in optical sensing and is critical for a variety of
industrial, military and scientific applications, including monitoring and controlling
manufacturing process, optical communication, biological and military night time sensing.
Carbon nanotubes (CNTs) are promising candidates for future IR detectors due to their unique
band structure, excellent electronic and optoelectronic properties, and super mechanical and
chemical stabilities. Moreover, the band gap of a semiconducting single-walled carbon
nanotube (SWCNT) is tunable by changing its diameter and chirality [1]. CNTs not only
present excellent electrical properties, ballistic transport, ohmic contact with electrodes and
ultrahigh carrier mobility [2,3], but also exhibit strong infrared light absorption with broad
band and fast light response up to picoseconds [4,5]. The absorption coefficient of SWCNT is
at least one order of magnitude larger than that of mercury-cadmium-telluride, the most
popular photoconductor for two-dimensional (2D) photodetector arrays, and over 70%
incident radiation can be absorbed by a SWCNTs film with a thickness of 100 nm [6]. A
commercial semiconductor based IR photodetector usually possesses a very fast response and
high detectivity up to 1012 Jones (1 Jones = 1 cm Hz1/2/W) [7], but it needs to be cooled to low
temperature which limits its applications. It would be advantageous to design a low cost CNT
based photodetector with high quantum efficiency, high sensitivity and high speed over the IR
spectral range without cooling. Additionally, with an important predominance due to its
exceptional mechanical flexibility, CNT IR detector may be readily implemented on a flexible
substrate at a low cost that is not possible for traditional group III-V semiconductors.
CNT photodetectors were previously developed based on both such thermal and photo
effects. In a typical thermal detector, such as a bolometers [6,8–10] or thermopile [11], an
electrical signal (resistance, current or voltage) was produced by temperature change due to
the illumination. While in a photo detector, such as in a photoconductive detector or p-n
junction photodiode, excitons are generated by interband transition via photon absorption of
CNTs and electron-hole pairs are set free by excitons dissociation, resulting a photocurrent or
photovoltage in the device [2]. The main difference for IR applications using these two
mechanisms is the way that the electric signals are generated and affected by the interaction
with the CNT.
Significant progresses have been made in recent years on CNT IR bolometers [8–10].
Most of the reports focus on the bolometer made of CNT films with a thickness more than
tens of nanometers [6,9,10]. The energy absorption of the film is sufficient, but the device
performance is usually seriously influenced by the surroundings. It was concluded that
SWCNTs film should be suspended in vacuum environment to prevent heat dissipation. In
additional, the performance of the CNT bolometer usually degrades with increasing
temperature and some of them do not work at room temperature due to the significantly
decreased signal-to-noise (S/N) ratio at room temperature [6]. Another significant drawback
of such bolometers is that the change of conductivity is typically below 1% level and is
therefore difficult to measure. The photoconductivity of the SWCNT based field effect
transistor (FET) was also investigated but the photoresponse current was typically of the pA
level even under a strong laser illumination of approximately 1 kW/cm2 due to the symmetric
built-in field in two contact areas resulting in low collection efficiency of photoexcited
carriers [12]. Furthermore, both bolometers, which are dominated by thermal effect, and FETs
which work by the exciton separation need a bias voltage to IR response measurement which
also increases the power consumption of the system.
In principle photovoltaic IR detectors based on p-n diode or p-i-n diode can work under
zero voltage or current as self-powered device without external power supply. While there
exist many reports on CNT diodes, most of the CNT diodes were based on split gates,
chemical doping and asymmetric contacts [13–16]. In this work we use a SWCNT based
barrier-free bipolar diode (BFBD) device structure which is basically an asymmetrically

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contacted CNT, with one end being contacted by Pd (p-contact) and the other end being
contacted by Sc or Y (n-contact). This device structure is simple, involves only doping-free
fabrication process, but exhibits excellent IR photo response [17–20]. However, light
absorption of a single SWCNT is too weak to be useful for practical weak IR detection. In our
earlier report, thin film BFBDs were fabricated using SWCNT submonolayer network, but the
multiple CNT-CNT junctions in the network degraded the device performance [21]. More
recently a method for growing CNT arrays on the monocrystal quartz substrate was
developed, yielding perfectly assigned SWCNT arrays along certain crystal orientations [22–
24]. The growth and transfer of these CNT arrays have been realized in wafer-scale, with the
highest density of CNTs up to 60 tubes/µm, and a ratio of semiconducting CNTs of up to 95%
[25,26]. It is expected that such parallel CNT arrays should lead to better device performance
than that based on the network due to the absence of CNT-CNT junctions between CNTs in
the parallel arrays. In this paper, we aim to demonstrate that photodiodes based on well-
aligned CNT array are well suited for IR detection. In particular our experimental results show
superior performance advantages of the CNT BFBD based IR detectors over that based on
thermal effects, and a large photo photoresponsivity ~9.87 × 10−5 A/W and detectivity ~1.09 ×
107 cmHz1/2/W.
2. Experimental
SWCNT arrays used in this work were grown by chemical vapor deposition (CVD) on
monocrystal quartz and transferred to silicon wafer covered with 500 nm thermally grown
SiO2. The CNT density is about 2-3 tubes per micron after transfer. The CNT arrays were cut
into stripes with a width W = 20 µm (perpendicular to CNTs) by using electron beam
lithography and O2 plasma etching, and the lengths of the stripes were adapted to the channel
lengths. All electrodes were patterned by electron beam lithography and deposited by electron
beam evaporation. All transport measurements were carried out using Keithley 4200
semiconductor analyzer at room temperature. Photovoltaic measurements were carried out
using a laser with λ = 785 nm and the power density of the focused laser beam on the device
may be varied from 0 to 1.57 kW/cm2.

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 Fig. 1. Fabrication of the asymmetrically contacted CNT thin film diode. (a) Low and (b) high
magnification SEM images of the aligned SWCNTs grown on quartz. (c) Arrays of SWCNTs
on Si/SiO2 substrate after being transferred from quartz. (d) Typical SEM image of thin film
diode contacted with Sc and Pd as source and drain respectively, with channel width W = 20
µm and channel length L = 1 µm.

3. Results and discussion

Shown in Figs. 1(a) and 1(b) are scanning electron microscopy (SEM) images of different
magnifications showing perfectly aligned CNT arrays as grown on quartz. These CNT arrays
are synthesized by chemical vapor deposition (CVD) as described in early reports [24–26].
The CNTs on the quartz are more than 100 µm in length and 1-2 nm in diameter with a
density of 2-3 tubes per micron. Due to the presence of both metallic (M) and semiconducting
(S) nanotubes in the CNT arrays, it is necessary to remove the metallic pathway spanning the
channel of the devices used for IR detection here. Since it is difficult to remove the metallic
CNTs in the channel for the devices fabricated directly on quartz substrate [27], CNTs were
transferred from quartz to Si/SiO2 or other substrate, on which we can apply an appropriate
back-gate to turn off semiconducting CNTs and breakdown metallic ones using a large bias
current [21,28]. CNT arrays are transferred via poly (methyl methacrylate) (PMMA)-mediated
approach, which has been used for transferring nanomaterials, such as CNT, zinc oxide,
graphene with simple process and high repeatability [29]. Figure 1(c) is a representative SEM
image showing the transferred CNT arrays on a Si/SiO2 substrate, and Fig. 1(d) is a SEM
image showing a typical photodiode fabricated by asymmetric contact on one end of the as-
transferred CNT array channel with Sc and on other end with Pd. We note that the density of
CNTs does not decrease significantly during the transfer and fabrication process.

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 Fig. 2. Electrical properties of CNT thin film FET and diode devices. (a) Schematic diagrams
showing the fabrication process of the diode. Starting from a p-type FET with Pd contacts, Sc
extension is deposited on one of the Pd contact to transfer it into an n-type contact, followed by
PMMA coating for passivation. (b) Transfer characteristics of a typical p-type CNT thin film
FET (with W = 20 µm and L = 1.5 µm) before and after electrical breakdown, and
corresponding (c) output characteristics after breakdown. (d) Transfer characteristics and (e)
linear and logarithm (inserted Fig.) I-V characteristics of the diode device (W = 20 µm and L =
1 µm). The channel length is reduced after adding Sc extension and PMMA passivation to the
initial p-type FET.

To fabricate BFBD devices, the as-transferred SWCNT arrays were cut into stripes prior
to electrode depositions and unwanted nanotubes outside the device channel region are
removed via electron beam lithography (EBL) and oxygen plasma etching process. Figure
2(a) illustrates the brief fabrication process of the asymmetrically contacted photodiode which
is based on the as-made SWCNT array stripe. The process begins with the fabrication of a p-
type FET. The two Pd electrodes with a thickness of 50 nm are patterned by EBL and
deposited by electron beam evaporation to act as the p-type source and drain electrodes of the
CNT FET, and the 500 nm silicon dioxide beneath the device is used as the back-gate
dielectric. Figure 2(b) shows typical p-type transfer characteristics measured from a CNT FET
(with L = 1.5 µm and W = 20 µm) before and after metallic nanotubes breakdown. The as-
made FET device exhibited a very low current on/off ratio of about 2, but the ratio was
improved to be more than 105 after metallic CNT breakdown. The corresponding output
characteristics show clearly linear dependence of the device current on the voltage (see Fig.

#165364 - $15.00 USD Received 23 Mar 2012; revised 20 Apr 2012; accepted 24 Apr 2012; published 23 May 2012
(C) 2012 OSA 1 June 2012 / Vol. 2, No. 6 / OPTICAL MATERIALS EXPRESS 844
2(c)) at low bias, showing that ohmic contacts are formed between CNTs and Pd electrodes
after breakdown process. The on-current density of this FET is about 4 µA / µm at bias Vds =
2 V.
To convert the p-type CNT FET into a diode, a 500 nm Sc extension into the channel is
patterned on one of the Pd electrodes of the as-made p-type FET by EBL (Fig. 2(a)). The Sc
extension acts as the n-type contact to the CNT array, and the channel length is reduced from
original 1.5 µm (for the p-type FET) into 1 µm. In this new device, the CNT array channel is
contacted asymmetrically by Pd and Sc. The Pd electrode is aligned with the valence band of
the semiconducting CNT to allow high efficient holes injection into the channel without
barrier, while the Sc electrode is aligned with the conduction band of the CNT and forms
ohmic contact with the CNT for barrier-free electrons injection [17,20]. In order to increase
the long-time stability of the as-fabricated device, the diode is covered with a PMMA coating
as passivation layer. Figure 2(d) shows the transfer characteristic of the diode coated with a
PMMA passivation layer, exhibiting a typical ambipolar characteristics of an ambipolar FET
with an off-state at a gate voltage of approximately 0 V. This is a preferred feature for real PV
applications, since the coated diode with off-state at zero gate voltage has the largest power
conversion efficiency [18]. The two-terminal I-V characteristic of the diode is shown in Fig.
2(e), exhibiting excellent rectifying behavior. The rectification ratio (i.e., on-current at bias of
2 V divided by the absolute value at bias of −2 V) approaches 104, which is much higher than
that reported before for diodes based on aligned CNT arrays [30].
The uniformity of CNT diode devices is an important merit for large area IR detector
applications. The characteristics of the devices based on individual semiconducting CNTs are
usually significantly different from each other due to the variations on CNT diameters and
chiralities. However, the uniformity of devices based on CNT arrays with sufficient number of
tubes in the channel is much better than based on a single CNT because the characteristics for
the arrays are determined by the average among all the nanotubes participating in the
transport. In this work, FETs and diodes with the same device dimensions exhibit almost the
same characteristics, including the current on/off ratio, on state current, threshold voltage and
rectification ratio. As shown in Fig. 3, ten FETs (each single FET with L = 1.5 µm and W = 20
µm) and diodes (with L = 1.0 µm and W = 20 µm) were fabricated and connected in parallel.
The device current for both the parallel connected 10 FETs and 10 diodes with PMMA
coating are about 10 times that of the single device (see Figs. 3(a) and 3(d)). The optic image
of the device formed by 10 diodes connected in parallel is showed in Fig. 3(e). Since there no
CNT-CNT junctions for the parallel aligned nanotubes in the channel, the electrical
breakdown process is highly controllable resulting in a high devices yield. This is important
for successfully fabricating large scale or parallel devices.

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 Fig. 3. Transfer and output characteristics of ten parallel CNT FETs and diodes. (a) Transfer
characteristics of a device composed of ten parallel connected p-type CNT thin film FET (with
W = 20 µm and L = 1.5 µm) before and after electrical breakdown, and corresponding (b)
output characteristics of the device. (c)Transfer characteristics and (d) I-V characteristics of a
device (W = 20 µm and L = 1 µm) composed of ten parallel connected CNT diodes. (e) Optical
image showing ten parallel CNT diodes device.

Figure 4(a) shows an optical image of a real CNT array diode. A built-in electric field is
formed along the nanotubes due to the asymmetrically contacted n-type (Sc) and p-type (Pd)
electrodes, which is essential for a photodetector to efficiently separate photogenerated
electrons and holes [17,20]. Because the channel length (~1 µm) is of the same length scale as
the thickness of the back gate dielectric (SiO2), the band bending of the nanotubes extends
through the device due to the weak coupling between the channel and bake-gate.
Consequently, the built-in field is spread over the whole channel which is highly desirable for
electron-hole separation [31]. Under illumination, the photogenerated electron-hole pairs are
separated by the built-in field and collected by the source and drain electrodes, resulting in
photovoltage and photocurrent as shown in Fig. 4(b). In our photoresponse measurements, the
Sc electrode is always grounded and the bias is applied on the Pd electrode. When the bias V
is equal to the open circuit voltage VOC, the photocurrent and the dark current cancel each
other and result in a zero net current. The ISC and VOC of the device are 10.94 nA and 0.24 V
respectively under 785 W/cm2 illumination, and increased to 21 nA and 0.25 V when the

#165364 - $15.00 USD Received 23 Mar 2012; revised 20 Apr 2012; accepted 24 Apr 2012; published 23 May 2012
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power density increased to 1570 W/cm2. The incident power density dependent ISC and VOC
are shown in Fig. 4(c).
While ISC increases linearly with increasing power density, VOC increases logarithmically
with increasing incident light intensity, exhibiting typical photodiode behaviors. When
compared with diodes based on individual CNT, about 1/20 illumination power density is
needed for thin film diode to yield similar photocurrent and photovoltage, indicating that there
remain approximate 20 semiconducting tubes in the device channel after electric breakdown.
The more nanotubes present in the channel the more carriers and thus photocurrent will be
produced under the same illumination density. This makes the photocurrent signal of a thin
film diode more detectable under lower power density. From Fig. 4(c), it can be readily
estimated that IR photo responses are detectable at 157 mW/cm2, which is at least one order of
magnitude lower than that of the diode based on a single CNT. Figure 4(d) shows the repeated
photoresponse of the diode under the same power densities. We can see that ISC of the diode is
stable and repeatable during long time measurement, indicating that this device is reliable for
application in photovoltaic IR detection.

Fig. 4. Photovoltaic and electronic characteristics of a typical CNT thin film diode. (a) Optical
image showing a CNT diode with channel length L = 1 µm. (b) I-V characteristics of the diode
measured in dark and under illuminations. (c) Experimental data and fitted results for open
circuit voltage and short circuit current as a function of illumination power density. (d)
Photoresponse of the CNT IR detector under different illumination densities.

One of the basic metrics for evaluating photovoltaic detector is external quantum
efficiency (EQE), defined as the number of carriers produced per photon, i.e.,
η = ( I ph / q ) ( hυ / Pin ) [32], where Iph is the photocurrent or ISC at the zero bias condition, q is
electron charge, h is the Planck constant, υ is the frequency of light, and Pin is the incident
power. The EQE η of the CNT array diode is estimated to be about 0.0156% for Iph = 3.1 pA
under 157 mW/cm2. The relatively low level of EQE is ascribed to the small effective
absorption cross section of the CNTs in the channel. If Pin is estimated by considering the total

#165364 - $15.00 USD Received 23 Mar 2012; revised 20 Apr 2012; accepted 24 Apr 2012; published 23 May 2012
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area of the CNT sections perpendicular to the incident direction as the actual effective
absorptive area, η of the diode then raises to 10.4%, coinciding with previous reports [2].
To access the sensibility of the CNT array based photovoltaic IR detector, two parameters
*
are calculated: the current responsivity R = I ph / Pin and the detectivity D = R A / in
[32,33]. Here A is the active area of the detector and in is the root-mean square current noise
per bandwidth. In the zero bias condition, Iph is equal to ISC. The maximum R of our
experiments is ~9.87 × 10−5 A/W, which raises to 6.58 × 10−2 A/W based on the actual area of
CNTs.
There are three contributions to the noise powers in2 that limit detectivity D*: thermal
noise, shot noise from dark current and flicker noise. On the basis of the dark current
characteristics of the CNT array diode, the total noise is primarily thermal in origin under zero
bias condition. The noise may be given as in = 4k BT / RD , where kB is the Boltzmann
constant, T is temperature, and RD is zero-bias differential resistance of the diode, at room
temperature T = 300 K and RD ~1 GΩ, in is estimated to be 4.07 × 10−15 AHz-1/2. As a result,
the room temperature detectivity D* is calculated to be ~1.09 × 107 cmHz1/2/W, which
outperforms the maximum detectivity of CNT-based bolometers which is of the order of 106
cmHz1/2/W [9,10].
While the CNT array diode shows promise for IR detection, the device may be further
improved significantly by increasing the density of semiconducting CNTs (dCNT) in the
channel. First, the more CNTs exist in the channel, the more efficiently the photons will be
absorbed and the weaker irradiation is needed to generate sufficient signal for detection.
Second, under the same illumination, the average internal quantum efficiency of each CNT is
similar and then the external quantum efficiency of the diode increases linearly with dCNT.
This suggests that the responsivity of the detector will be proportional to the number of the
CNTs. On the other hand, the resistance of the diode RD will be reduced with increasing CNTs
in the channel, and the thermal noise is inversely proportional to RD1/2, thus the noise will be
increased linearly with the dCNT1/2. Therefore, the detectivity D* is proportional to the dCNT1/2
when the noise is dominated by thermal noise. The density of CNTs can be raised by
controllable growth or multiple transfers [25,34,35]. Here we just discuss a possible ideal
growth result based on existing reports. If the CNTs reach 60 tubes per micron and 95% of
them are semiconducting as mentioned above, the amount of active CNTs in the channel is
about 60 times of the present device. It is believable that the responsivity of CNT IR detector
would then be improved one or two orders of magnitude up to ~10 mA/W and the detectivity
would be nearly one order of magnitude larger and reach ~108 cmHz1/2/W.
In summary, this report demonstrates CNT arrays based high performance IR detector
with a responsivity of 9.87 × 10−5 A/W and a detectivity > 107 cmHz1/2/W. The doping-free
process utilized for fabricating the CNT array diodes has compatibility with Si based
technology, allowing wafer-scale CNT IR detector be integrated with CMOS integrated
circuits, including readout circuits. This type of IR detector preserves the potential advantage
desired for cost-effective, lightweight, and compact IR photodetectors, with additional
advantages on simple device fabrication and un-cooled IR detection at room temperature.
Acknowledgments
This work was supported by the Ministry of Science and Technology (Grant Nos.
2011CB933002, 2011CB933001, and 2012CB932302), the National Science Foundation of
China (Grant Nos. 61001016, 51072006, 90921012, and 51172271), and Beijing Municipal
Education Commission (Grant No. YB20108000101). Work at Duke is in part supported by a
grant from ONR (N00014-09-1-0163) and a grant from RF nano Inc. JL and WZ also
acknowledge the Shared Materials Instrumentation Facility (SMIF) at Duke University for
access to their instrumentation.

#165364 - $15.00 USD Received 23 Mar 2012; revised 20 Apr 2012; accepted 24 Apr 2012; published 23 May 2012
(C) 2012 OSA 1 June 2012 / Vol. 2, No. 6 / OPTICAL MATERIALS EXPRESS 848