Iodine doping effects on the lattice thermal conductivity of oxidized polyacetylene

nanofibers
Kedong Bi, Annie Weathers, Satoshi Matsushita, Michael T. Pettes, Munju Goh, Kazuo Akagi, and Li Shi

Citation: Journal of Applied Physics 114, 194302 (2013); doi: 10.1063/1.4831945
View online: http://dx.doi.org/10.1063/1.4831945
View Table of Contents: http://scitation.aip.org/content/aip/journal/jap/114/19?ver=pdfcov
Published by the AIP Publishing

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Iodine doping effects on the lattice thermal conductivity of oxidized
polyacetylene nanofibers
Kedong Bi (),
1,2,a)
Annie Weathers,
2
Satoshi Matsushita,
3
Michael T. Pettes,
2
Munju Goh,
3,4
Kazuo Akagi,
3
and Li Shi
2,a)
1
Jiangsu Key Laboratory for Design and Manufacture of Micro-Nano Biomedical Instruments,
School of Mechanical Engineering, Southeast University, Nanjing 211189, Peoples Republic of China
2
Department of Mechanical Engineering, University of Texas at Austin, Austin, Texas 78712, USA
3
Department of Polymer Chemistry, Kyoto University, Kyoto 615-8510, Japan
4
Institute of Advanced Composite Materials, Korea Institute of Science and Technology (KIST),
Eunha-ri san 101, Bondong-eup, Wanju-gun, Jeolabuk-do 565-905, Korea
(Received 22 September 2013; accepted 3 November 2013; published online 18 November 2013)
Thermal transport in oxidized polyacetylene (PA) nanobers with diameters in the range between
74 and 126 nm is measured with the use of a suspended micro heater device. With the error due to
both radiation and contact thermal resistance corrected via a differential measurement procedure,
the obtained thermal conductivity of oxidized PA nanobers varies in the range between 0.84 and
1.24 Wm
1
K
1
near room temperature, and decreases by 40%70% after iodine doping. It is also
found that the thermal conductivity of oxidized PA nanobers increases with temperature between
100 and 350 K. Because of exposure to oxygen during sample preparation, the PA nanobers are
oxidized to be electrically insulating before and after iodine doping. The measurement results
reveal that iodine doping can result in enhanced lattice disorder and reduced lattice thermal
conductivity of PA nanobers. If the oxidation issue can be addressed via further research to
increase the electrical conductivity via doping, the observed suppressed lattice thermal
conductivity in doped polymer nanobers can be useful for the development of such conducting
polymer nanostructures for thermoelectric energy conversion. VC
2013 AIP Publishing LLC.
[http://dx.doi.org/10.1063/1.4831945]
I. INTRODUCTION
Due to their high exibility, light weight, and low cost,
polymers have been explored for diverse applications includ-
ing displays,
1
solar cells,
2
electronic packaging,
3
and recently
thermoelectric energy conversion.
4
In electronic packaging,
polymeric adhesives are commonly used as thermal interface
materials, where high thermal conductivity is desirable for
reducing the operating temperature of electronic devices. In
comparison, the low thermal conductivity found in many
polymers has motivated the recent investigation of conducting
polymers as efcient thermoelectric materials. The thermo-
electric energy conversion efciency is characterized by the
gure of merit ZT=S
2
rT/j, where S is the Seebeck coef-
cient, r is the electrical conductivity, T is the temperature, and
j is the thermal conductivity including a lattice contribution
and an electronic contribution. A low lattice thermal conduc-
tivity is desired to minimize the parasitic heat loss due to pho-
non transport between the hot and cold sides of thermoelectric
devices.
5
Therefore, the wide range of thermal transport
requirements for various polymer applications calls for an
enhanced capability in extending the upper and lower limits
of the thermal conductivity of polymers.
In theory, the thermal conductivity of a single polymer
chain can be high. For example, molecular dynamics simula-
tions
6
and ab initio calculations
7
have shown that the room-
temperature thermal conductivity of single polyethylene
chains can exceed 300 Wm
1
K
1
, which surpasses the val-
ues reported for many metals. However, when polymer
chains are entangled together to form bulk or thin lm poly-
mer materials, the thermal conductivity is greatly suppressed
due to the inter-chain interactions and random chain align-
ment.
8
Consequently, bulk and thin lm polymers are typi-
cally characterized with low thermal conductivity values on
the order of 0.1 Wm
1
K
1
near room temperature.
9
The
thermal conductivity can be increased by aligning the poly-
mer chains in the sample via mechanical stretching.
10
For
drawn polyethylene nanobers with a diameter of ~130 nm
and length of ~290 lm, one recent measurement based on
a bimaterial micro-cantilever thermometer has yielded a
room-temperature thermal conductivity as high as
104 Wm
1
K
1
.
11
In comparison, a time-domain thermore-
ectance (TDTR) measurement has yielded a thermal con-
ductivity value of about 20 Wm
1
K
1
for polyethylene
bers with diameters in the range between 10 and 30 lm.
12
The TDTR measurements also yield a decreased thermal
conductivity with increasing temperature. This temperature
dependence reveals that the thermal conductivity is limited
by intrinsic lattice anharmonicity instead of lattice disorders.
However, the TDTR method has not been able to obtain the
temperature-dependent thermal conductivity of nanobers
with diameter smaller than that of the micron-sized laser
beam. Meanwhile, only the room-temperature thermal con-
ductivity has been obtained from the measurement based on
the bimaterial micro-cantilever sensor.
11
Hence, comprehen-
sive thermal conductivity measurements of organic nanob-
ers have remained an open challenge.
a)
Authors to whom correspondence should be addressed. Electronic mail:
lishi@mail.utexas.edu; kedongbi@seu.edu.cn
0021-8979/2013/114(19)/194302/6/$30.00 VC
2013 AIP Publishing LLC 114, 194302-1
JOURNAL OF APPLIED PHYSICS 114, 194302 (2013)
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In addition, these recent works on thermal transport in
polymer chains and bers have been focused on polyethylene
and a limited number of other polymer systems, whereas the
thermal conductivity of nanobers of many other polymer
systems has remained elusive. One notable example is polya-
cetylene (PA), one of the simplest conjugated organic con-
ducting polymers. The electrical conductivity of PA can be
enhanced dramatically by more than seven orders of magni-
tude after doping,
13
and has been reported to be up to
15 0000 Scm
1
at room temperature after doping with io-
dine.
14
PA consists of a carbon backbone connected with
alternating single and double bonds and terminated with
hydrogen. Because the double bonds in PA are stronger than
the single carbon-carbon bonds in polyethylene, molecular
dynamics simulations have suggested that the thermal con-
ductivity of a pristine PA chain can be 2.6 times higher
than that of polyethylene.
15
The effects of stretching and or-
dered mixing of polymer chains on the thermal conductivity
of PA have also been studied by molecular dynamics simula-
tions.
16,17
There have been a number of thermal conductivity
measurements of PA sheets. For example, Moses and
Denenstein reported a thermal conductivity measurement of
pure and heavily doped PA sheets.
18
They suggested that ear-
lier reports of large thermal conductivity in PA samples were
caused by large radiation errors in the measurements. With
radiation errors corrected, their measurement results sug-
gested that the lattice thermal conductivity increased
from 0.21 Wm
1
K
1
for cis-(CH)
x
to 0.38 Wm
1
K
1
for
trans-(CH)
x
after isomerization. In addition, the measured
total thermal conductivity increased to 0.69Wm
1
K
1
after
the sample was doped to the metallic regime with a conduc-
tivity value of 270S cm
1
. The increase in the thermal con-
ductivity exceeded by about 62% the electronic contribution
calculated with the Wiedemann-Franz (W-F) law from the
measured electrical conductivity based on the Lorenz number
of a metal. Because it remains an open question whether the
Wiedemann-Franz law is still applicable to conducting poly-
mers, it is unclear whether the chemical doping could have
increased the lattice thermal conductivity of the PA sheets.
Moreover, while there have been a number of electron trans-
port studies of PA nanobers, there have not been reports of
experimental studies on their thermal conductivity.
Here, we report temperature-dependent thermal conduc-
tivity measurements of PA nanobers of different lengths
and diameters with the use of a suspended micro-device with
built-in resistance thermometers. As two unique features of
the measurement, a differential measurement method is
established to eliminate the error caused by parasitic heat
transfer via radiation and residual gas molecules in the sam-
ple space, and the contact thermal resistance is determined
from the length dependence of the measured thermal resist-
ance of the nanobers. In addition, results from energy-
dispersive X-ray spectroscopy (EDX) suggest the presence
of oxygen in the nanobers that have been exposed to air
during sample preparation. The measured thermal conductiv-
ity of the PA nanobers increases with temperature between
100 and 350 K. Moreover, the measurements show that io-
dine doping results in a pronounced further suppression of
the thermal conductivities of PA nanobers. The reduction
increases with increasing exposure time of the PA nanobers
to iodine. This previously unknown doping effect on the lat-
tice thermal conductivity is attributed to phonon scattering
by additional defects and impurities created by the iodine
doping.
II. EXPERIMENTAL METHODS
Helical PA lms were synthesized in chiral nematic liq-
uid crystals under an atmosphere of acetylene gas of six-nine
grade within a Schlenk ask immersed in an 8

C tempera-
ture bath.
19
Following synthesis, the PA lms were removed
from the ask and washed with a toluene/methanol solution
containing 1N hydrochloric acid, which is the same as 1M
hydrochloric acid, and with tetrahydrofuran in turn at ambi-
ent temperature. The lms were then sonicated for several
hours in ethanol at room temperature.
20
A small piece of PA
lm was separated into a large amount of single nanobers
after sonication. With the use of a micromanipulator with a
sharp tungsten tip, a single PA nanober was picked up and
placed between the two membranes on the device, as shown
in Figure 1 for one representative sample. The samples were
exposed to the atmosphere for several hours during the sam-
ple preparation process.
The thermal conductance measurements were carried
out with the use of a microdevice consisting of two adjacent
SiN
x
membranes each patterned with a serpentine platinum
resistance thermometer (PRT). The sample was placed in an
evacuated cryostat during the thermal measurement. When
one PRT was heated with an electrical current, heat transfer
through the nanober raised the temperature of the other
sensing PRT. The temperature rise on each PRT was deter-
mined based on the measured electrical resistance and the
calibrated temperature coefcient of resistance of the PRT.
The thermal resistance of the long Pt/SiN
x
beams connecting
the two SiN
x
membranes to the substrate was determined
from the electrical heating rate and the corresponding tem-
perature rise of the two PRTs. The heat conduction rate
through the nanober was the same as that in the six Pt/SiN
x
beams connected to the sensing membrane, which was deter-
mined based on the measured temperature rise of the sensing
PRT and the thermal resistance of the six beams. The ther-
mal resistance of the nanober was determined based on the
heat conduction in the nanober and the measured tempera-
ture difference between the two PRTs. The details and data
analysis of this two-probe steady state thermal measurement
method could be found in a previous publication.
21
In order to eliminate the errors caused by background
heat transfer between the two PRTs via residual gas mole-
cules and radiation, a differential measurement method was
devised. In this method described in detail elsewhere,
22
the
temperature rise on the sensing PRT of the nanober sample
was measured relative to the temperature rise on a sensing
PRT of a blank reference device without a nanober. Both
devices were fabricated on the same chip and had the same
geometric design. This method yielded the thermal conduct-
ance of the nanober sample, without contribution from par-
asitic heat transfer via radiation and residual gas molecules
between the two thermometers. This feature was similar to
194302-2 Bi et al. J. Appl. Phys. 114, 194302 (2013)
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210.94.171.100 On: Fri, 28 Mar 2014 11:57:47
that of the macroscale measurement reported by Moses and
Denenstein for the measurement of thin PA sheets.
18
One
advantage of our miniaturized version of this measurement
was that the two thermometers were thermally isolated from
the environment by the long suspended beams, so that a sam-
ple thermal conductance as small as 1 10
10
W K
1
could
be measured. The thermal conductance of the undoped nano-
ber samples exceeded 1.4 10
9
W K
1
at room tempera-
ture, which was several times higher than the background
conductance measured on a device without a nanober
sample.
While parasitic heat transfer via residual gas and radia-
tion between the two thermometers could result in an overes-
timated sample thermal conductivity if it were not corrected,
parasitic heat loss from the circumference of the nanober to
the environment via radiation and residual gas molecules
could result in an underestimated sample thermal conductiv-
ity. With radiation loss from the circumference of the nano-
ber taken into account and the temperature rise in the
sensing membrane considered to be much smaller than that
in the heating membrane, the thermal resistance of the nano-
ber could be calculated as
23
R
s
=
1

p
2
erjT
3
d
3
_
sinh bL
cosh bL
; (1)
where b =

16erT
3
=jd
p
, j, L, and d were the thermal con-
ductivity, suspended length, and diameter of the nanober, T
was the average temperature of the system, e was the surface
emissivity. For bL 1, Eq. (1) was reduced to the following
conduction expression of the diffusive thermal resistance:
R
s
=
4L
pjd
2
: (2)
The relative error in neglecting the radiation loss in
Eq. (2) was thus
D =
bL cosh bL
sinh bL
1: (3)
As shown in a recent work,
22
for small bL 1, D was
reduced to (bL)
2
/2. In addition, for a constant aspect ratio,
L/d, and emissivity, e, this relative error decreases with L.
The emissivity can also decrease when the diameter of the
nanober is less than the radiation penetration depth. Hence,
radiation loss from the circumference of the nanober in this
microscale measurement could be orders of magnitude
smaller than the macroscopic measurement of PA sheets by
Moses and Denenstein.
18
Based on a bulk e ~0.3, D was cal-
culated to be less than 0.2% for all the PA samples measured
in this work.
III. RESULTS AND DISCUSSION
A total of six samples have been measured in this work.
As summarized in Table I, the diameters of the samples
range between 74 and 126 nm, with the suspended length in
the range between 1.86 and 7.15 lm. Figure 1 shows a scan-
ning electron microscopy (SEM) image of a representative
sample with diameter 74 66 nm and suspended length
2.36 60.01 lm. It is worth noting that the lateral dimension
of the PA nanober was measured from the top-view SEM
images. Titled SEM measurements were not conducted
because of concerns of electron beam charging and damage
of the electrically insulated PA nanobers by extensive SEM
measurements. Consequently, the cross section of the nano-
bers has been assumed to be circular, which can cause addi-
tional uncertainties in the obtained thermal conductivity
results.
The thermal contact resistance (R
c
) between the nano-
ber and the membranes of the suspended device is expected
to add an additional contribution to the measured thermal re-
sistance, R, as
R = R
c
R
s
; (4)
where R
s
is the intrinsic thermal resistance of samples. The
contact resistance is inversely proportional to the contact
width, which is proportional to the diameter of the measured
FIG. 1. SEM images of a suspended
device with a PA nanober across the
two membranes. The scale bar is 7 lm
in (a) and 800 nm in (b). The diameter
and suspended length for this PA4 sam-
ple are 7466 nm and 2.3660.01lm,
respectively.
TABLE I. Dimensions of the measured suspended PA nanobers.
Diameter
[nm]
Suspended
length [lm]
Iodine exposure
time [h]
PA1 121 611 7.15 60.01 120
PA2 85 69 1.86 60.01 5
PA3 126 622 7.12 60.01 22
PA4 74 66 2.36 60.01
PA5 100 65 1.94 60.01
PA6 114 615 2.88 60.01
194302-3 Bi et al. J. Appl. Phys. 114, 194302 (2013)
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210.94.171.100 On: Fri, 28 Mar 2014 11:57:47
sample.
24
Figure 2 shows the measured thermal resistance,
R, versus L/d
2
at 305 K and 107 K for four samples with the
diameter in the range between 100 and 126 nm. Linear tting
of the data extrapolates to a small residual resistance value at
L=0. This small intercept suggests that the contact resist-
ance is small compared to the diffusive thermal resistance,
particularly for the longest samples with the largest thermal
resistance values.
Because the contact resistance is small compared to the
diffusive resistance of the nanober and because radiation
heat losses in the nanober and the supporting beams are
negligible compared to the heat conduction through the sam-
ple in the temperature range of the measurements,
23,25
the
thermal conductivity has been calculated from the measured
thermal resistance as j =4 L/pd
2
R. The as-obtained thermal
conductivity before iodine doping of two PA nanober
samples with the longest suspended length is shown in
Figure 3(a) as a function of temperature. The thermal con-
ductivity increases with increasing temperature, and reaches
a value of about 0.9 Wm
1
K
1
at 350 K. The temperature
dependence and relatively low magnitude of the thermal con-
ductivity suggest that the thermal conductivity of the nano-
bers has not reached the intrinsic limit governed by lattice
anharmonicity, which was recently attained in some high-
modulus bers where the thermal conductivity is found to be
as high as 20 Wm
1
K
1
at 300 K and decreases with
increasing temperature. The temperature dependence
observed in these PA nanobers of relatively low thermal
conductivity is not caused by radiation heat transfer between
the heating and sensing membranes, which has been elimi-
nated by the differential measurement method. Instead, the
result is attributed to disorders and defects still present in the
nanober samples, which are responsible for the much lower
values measured here than those calculated for defect-free
single PA chains and aligned PA nanobers. However, it is
difcult to characterize the internal morphology and defects
in the nanobers via electron microscopy techniques. In
addition, thermal measurements at temperatures lower than
100 K were not conducted because new low-dimensional
transport phenomena are not expected in the defective nano-
ber systems in the low temperature regime.
Figure 3(b) shows the thermal conductivity as a function
of the diameter, which is nearly constant across the diameter
range measured. This result suggests that the chain alignment
in the nanober does not correlate with the nanober diame-
ter for the samples measured in this work. The thermal con-
ductivity values of the six PA nanobers are in the range
between 0.84 and 1.24 Wm
1
K
1
at 305 K, which is higher
than that of non-oriented pristine bulk PA lms measured
nearly 30 years ago by two independent groups, which are
0.4 Wm
1
K
1
and 0.38 Wm
1
K
1
, respectively.
18,26
In
comparison, a value of about 13 Wm
1
K
1
at room temper-
ature has been reported for an oriented undoped cis rich-PA
lm.
27
However, this high thermal conductivity value yielded
a phonon mean free path larger than 100 nm, which is one
order of magnitude larger than the measured structure coher-
ence length. Therefore, the temperature dependence and the
room-temperature thermal conductivity in the range between
0.84 and 1.24 Wm
1
K
1
reveal that phonon transport is
dominated by scattering by structural disorders, such as oxy-
gen impurities discussed below, random chain alignments,
and inter-chain interactions, instead of lattice anharmonicity.
To investigate the effects of iodine doping, we have
measured the thermal conductivity of the PA nanobers
before and after exposure to iodine vapour in inert
atmosphere. During the iodine doping, the chip carrier,
FIG. 2. Measured thermal resistance versus L/d
2
of PA1, PA3, PA5, and
PA6 samples at 305 K and 107 K, where L and d are the suspended length
and diameter of the PA nanobers across the membranes. Linear ts extrap-
olate to 0.060 10
9
K W
1
and 0.169 10
9
K W
1
at zero suspended
length for 305 K and 107 K, respectively.
FIG. 3. (a) Measured thermal conductivity of the two samples PA1 and PA3
of the highest thermal resistance as a function of temperature, and (b) the
measured thermal conductivity for all six samples as a function of diameter
at 305 K and 107 K.
194302-4 Bi et al. J. Appl. Phys. 114, 194302 (2013)
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measurement device, and suspended nanober ensemble
were placed vertically in a Schlenk ask which was lled
with ~1 g of solid iodine akes. The ask was evacuated by
a mechanical pump and subsequently purged with argon
twice, and was maintained at room temperature for the entire
process. Following iodine exposure, a purple/brown lm was
adhered to the chip carrier and measurement device. The io-
dine exposure time was 120 h, 5 h, and 22 h for the three
samples studied. Figure 4 shows the ratio of the thermal con-
ductance of three samples before and after iodine doping,
which shows a reduction in thermal conductance of 40% or
more, with greater reduction for longer exposure time.
Previous reports showed that there was no observed
change
28,29
or an increase
18,26,30
of the thermal conductivity
of PA bulk lms upon iodine or AsF
5
doping. The increase
in the thermal conductivity was attributed to the thermal con-
ductivity contribution from charge carriers after doping.
18,30
In addition, the thermal conductivity of PA lms was meas-
ured in Ref. 30 to increase beyond what could be explained
with an increase of the electronic thermal conductivity based
on the W-F law. Moreover, it was found that the thermal
conductivity of PA lms became higher after they were com-
pensated into the insulating state by exposure to (CH
3
)
2
NH
atmosphere.
26
Hence, this unusual result is attributed to ei-
ther the inaccuracy of the W-F law in this system, or an
increase of the lattice thermal conductivity, which might be
possible as a result of the modication of amorphous and
crystalline regions upon the intercalation of the dopant.
In comparison, the PA nanobers investigated in this
work remain electrically insulating after iodine doping. The
samples studied here have been exposed to air for several
hours during the sample preparation and transfer process. It
has been reported
31
that brief oxygen exposure may decrease
the resistivity of pristine PA due to the doping effect of oxy-
gen. However, long-term exposure can result in an irreversi-
ble increase in the resistivity because of the formation of
carbonyl bonds, which interrupt the conjugation of the poly-
mer backbone. It has been shown that the electrical proper-
ties of bulk PA can be maintained for only a few minutes
upon exposed to oxygen.
32
Hence, the electrical conductivity
of PA exposed to oxygen for an extended time oxygen can
remain electrically insulating even after doping,
31
although
the electrical conductivity of PA that are not oxidized can be
increased considerably after doping. Moreover, PA nanob-
ers are expected to be more sensitive to oxygen exposure
owing to their large specic surface area. Such effect has
been demonstrated by measurements of an iodine-doped PA
ber network.
33
We have used EDX analysis to verify the
presence of oxygen in the nanober samples. As shown in
Figure 5, the EDX results reveal both oxygen and iodine
peaks for a sample doped with iodine. Therefore, the electri-
cally insulating feature of these PA nanobers upon iodine
doping is attributed to the relatively long exposure of the
sample to oxygen during the sample preparation.
Because the PA bers remain electrically insulating, the
measured thermal conductivity is expected to be dominated
by the lattice contribution. Hence, the observed reduction in
the thermal conductivity upon iodine doping unambiguously
shows that iodine doping results in disorder in the bond
strength as well as mass disorder in the backbone. The oxy-
gen absorbed into PA nanobers during the sample prepara-
tion could also reduce the lattice thermal conductivity.
IV. CONCLUSION
This experiment has addressed the challenge in
temperature-dependent thermal conductivity measurements
of organic nanobers with the use of a suspended micro-
device, where the radiation error and contact thermal resist-
ance error are corrected via the differential measurement
method for nanober samples of different lengths. The
obtained room-temperature thermal conductivity of the oxi-
dized PA nanobers before iodine doping is in the range of
0.84 and 1.24 Wm
1
K
1
, which is about a factor of 23
higher than those reported for non-oriented bulk PA
lms.
18,26
However, the obtained thermal conductivity is
insensitive to the nanober diameter in the range between 74
and 126 nm, suggesting no correlation between the polymer
chain alignment and the diameter of the measured samples.
In addition, because the measured thermal conductivity
increases with temperature between 100 K and 350 K, ther-
mal transport in the nanobers is still dominated by defects
FIG. 4. Ratio of the thermal conductance of the three samples PA1, PA2,
and PA3 as a function of temperature before and after iodine doping for
three different exposure times.
FIG. 5. EDX analysis of a PA nanober doped with iodine.
194302-5 Bi et al. J. Appl. Phys. 114, 194302 (2013)
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210.94.171.100 On: Fri, 28 Mar 2014 11:57:47
and disorders instead of the intrinsic lattice anharmonicity.
Moreover, it is found that doping with iodine can decrease
by as much as 70% the thermal conductivity of PA nanob-
ers. Because the polymer bers remain electrically insulating
upon doping due to exposure to oxygen, this nding shows
that the already low lattice thermal conductivity of the poly-
mer nanobers can still be reduced by chemical doping
which is used to increase the electrical conductivity. Such an
effect is desirable for the development of conducting poly-
mer nanostructures as efcient thermoelectric materials, pro-
vided that methods can be developed to prevent oxidation so
as to achieve a sufciently high and stable electrical conduc-
tivity upon doping.
ACKNOWLEDGMENTS
This work was supported by the U.S. National Science
Foundation (NSF) Award No. CBET-0933454. K.D.B. was
supported by the Natural Science Foundation of China
(Award No. 51205061), Natural Science Foundation of
Jiangsu Province (Award No. BK2012340), National Basic
Research Program of China (Award No. 2011CB707605),
and the Fundamental Research Funds for the Central
Universities. A.W. acknowledges support from the NSF
Graduate Research Fellowship Program. K.A. was supported
by Grants-in-Aid for Science Research (S) (No. 20225007)
and (A) (No. 25246002) from the Ministry of Education,
Culture, Sports, Science and Technology, Japan.
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