Carbon nanocone: A promising thermal rectifier

Nuo Yang, Gang Zhang, and Baowen Li

Citation: Appl. Phys. Lett. 93, 243111 (2008); doi: 10.1063/1.3049603

View online: https://doi.org/10.1063/1.3049603
View Table of Contents: http://aip.scitation.org/toc/apl/93/24
Published by the American Institute of Physics

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 APPLIED PHYSICS LETTERS 93, 243111 共2008兲

Carbon nanocone: A promising thermal rectifier

Nuo Yang,1 Gang Zhang,2,a兲 and Baowen Li1,3,b兲
1
Department of Physics and Centre for Computational Science and Engineering,
National University of Singapore, Singapore 117542, Singapore
2
Institute of Microelectronics, 11 Science Park Road, Singapore Science Park II,
Singapore 117685, Singapore
3
NUS Graduate School for Integrative Sciences and Engineering, Singapore 117597, Singapore
共Received 8 July 2008; accepted 19 November 2008; published online 15 December 2008兲
With molecular dynamics simulations, we demonstrate very obvious thermal rectification in large
temperature range from 200 to 400 K in nanocone. We also observe that the rectification of
nanocone does not depend on the length very sensitively, which is in stark contrast with the
nanotube thermal rectifier in which the rectification decreases dramatically as the length increases.
Our work demonstrates that carbon nanocone is a promising practical phononic device. © 2008
American Institute of Physics. 关DOI: 10.1063/1.3049603兴

Traditionally, information is carried and processed by
electrons and photons. Recently, phononic devices have been
brought forward theoretically, in which phonon, a heat pulse
through lattice, is used to carry and process information.1–7
Similar to electronic counterpart, the thermal rectifier also
plays a vital role in phononics circuit.7 The solid-state ther-
mal rectifier from carbon nanotubes 共CNTs兲 with nonuniform
axial mass distribution has been reported experimentally.8
Wu and Li9 also demonstrated the rectification in CNT
共n , 0兲 / 共2n , 0兲 intramolecular junctions using molecular dy-
namics 共MD兲 method. However, the rectifications in these
CNT junctions are much lower than that of electronic coun-
terparts. Moreover, in all theoretical models,1–4 the rectifica-
tion efficiency decreases quickly as the structure length in-
creases, which largely limits the application. In this letter, we
report another nanostructure—carbon nanocone—as a poten-
tial candidate for realistic thermal rectifier.
Carbon nanocone has a high asymmetric geometry.10 It
is characterized by the cone angle. Here we focus on the
cone with the cone angle of 113° 共see Fig. 1兲, which is the
largest angle observed experimentally10,11 and theoretically.12
In our simulations, classical nonequilibrium MD method
is adopted. The potential energy is a Morse bond and a har-
monic cosine angle for bonding interaction, which include
both two-body and three-body potential terms.13 This force
field potential is developed by fitting experimental param-
eters for graphite.14 The accuracy of Morse potential is tes-
tified by the calculation of thermal conductivity of a 40 nm
long 共10, 10兲 CNT with Morse potential: the value of
315 W / m K is very close to values 215– 350 W / m K
共Refs. 15–17兲 reported by others.
First, the heat flux in nanocone with 40 layers 共N = 40
and side face length is 5.6 nm兲 is explored. Here, fixed
boundary conditions are used. The nanocone is coupled with
Nosé–Hoover heat baths18,19 at the second and 共N − 1兲th lay-
ers, whose temperatures are Ttop and Tbottom, respectively. Be-
sides Nosé–Hoover heat bath, other methods can also be
used to produce a temperature gradient and calculate the heat
flux, such as the method developed by Müller–Plathe.15 Nev-
ertheless, it has been demonstrated that the heat flux calcu-
a兲
Electronic mail: zhangg@ime.a-star.edu.sg.
b兲
Electronic mail: phylibw@nus.edu.sg.
lated by MD does not depend on the details of the heat bath
used.4,15–17,20 In this letter, all calculations are done with the
same Nosé–Hoover heat bath parameter 共thermostat response
time兲 on the two ends.
The velocity Verlet algorithm is used to integrate the
differential equations of motions. In general, the temperature
TMD is calculated from the kinetic energy of atoms according
to the Boltzmann distribution.20 It is worth pointing out that
this approach is valid only at high temperature 共T Ⰷ TD, TD is
the Debye temperature兲. When the system temperature is
lower than the Debye temperature, it is necessary to apply a
quantum correction to the MD calculated temperature. The
difference between the MD calculated temperature and quan-
tum corrected temperature depends on the Debye tempera-
ture. However, the Debye temperature of nanocone is not
known. Although many theoretical studies have been con-
ducted on the Debye temperature of CNT, the results have
been controversial. For instance, 473,21 475,22 580,23 and
1000 K 共Ref. 24兲 are reported in different literatures. The
concerns of the current paper are the heat flux and rectifica-
tion effects 共a related change in heat flux兲, which do not
depend on the accurate value of temperature; instead they
depend only on the temperature difference. Therefore, we do
not do the quantum correction to TMD in this work. The heat
FIG. 1. 共Color online兲 Schematic picture of the carbon nanocone. d is the
distance from the atom to the center point in cone sheet. We define the atoms
in the ith layer as the atoms whose d 傺 关共i − 1兲rC , irC兴. The length along the
side face of nanocone is L = NrC, where N is the number of layers and rC is
the equilibrium carbon-carbon bond length.

0003-6951/2008/93共24兲/243111/3/$23.00 93, 243111-1 © 2008 American Institute of Physics

243111-2 Yang, Zhang, and Li
FIG. 2. 共Color online兲 共a兲 Heat flux J vs ⌬. 共b兲 Rectifications vs ⌬ for the
carbon nanocone. Here N = 40 and T0 = 300 K.
flux Jl along the nanocone is defined as the energy trans-
ported along the surface in unit time. The details can be
found in Ref. 25.
Simulations are performed long enough such that the
system reaches a stationary state. All results given here are
obtained by averaging 4 ⫻ 106 time steps. The time step is
0.4 fs. The total thermal conductivity contains contributions
from electrons and phonons. However, phonons dominate the
heat transport in nanocone because it is a semiconductor.12
In this letter, we set the temperature of top as Ttop
= T0共1 − ⌬兲 and that of bottom as Tbottom = T0共1 + ⌬兲, where T0
is the average temperature and ⌬ is the normalized tempera-
ture difference between the two ends. Therefore, the bottom
of nanocone is at a higher temperature when ⌬ ⬎ 0, and the
top has a higher temperature when ⌬ ⬍ 0. The heat flux J
versus temperature difference ⌬ 共corresponds to the I-V
curve of electric rectifier兲 is shown in Fig. 2共a兲. When ⌬
⬎ 0, the heat flux 共J兲 increases steeply with ⌬, while in the
region ⌬ ⬍ 0, the heat flux is much smaller and changes a
little with ⌬. That is, the nanocone behaves as a “good”
thermal conductor under positive “thermal bias” and as a
“poor” thermal conductor under negative thermal bias. The
heat flux runs preferentially along the direction of decreasing
diameter. The thermal rectification is defined as
共J+ − J−兲
R⬅ ⫻ 100%,
J−
where J+ is the heat current from bottom to top which cor-
responds to ⌬ ⬎ 0 and J− is the heat current from top to
bottom when ⌬ ⬍ 0. Figure 2共b兲 shows the rectifications with
different ⌬. The increase in ⌬ results in the increase in the
rectification ratio akin to the characteristic in electric recti-
fier.
In the thermal rectifier experiment,8 CNTs are gradually
deposited on the surface with heavy molecules to establish
asymmetric mass distribution. To increase the graded effects
in nanocone, we also studied the nanocone with the graded
mass distribution. The mass of the atoms of the ith layer is
set as M i = 关1 + 3共i − 1兲 / 共N − 1兲兴M C12, that is, the top atoms
have minimum mass 共M C12兲 and the bottom atoms have
maximum mass 共4M C12兲, where M C12 is the mass of 12C
atom. In Ref. 8, the atomic mass ratio is about 5 and the
Appl. Phys. Lett. 93, 243111 共2008兲
FIG. 3. 共Color online兲 关共a兲 and 共b兲兴 Rectifications and heat fluxes of carbon
nanocone at different temperatures T0 with fixed N = 40 and 兩⌬兩 = 0.5. 关共c兲
and 共d兲兴 Rectifications and heat fluxes for different lengths of carbon nano-
cone with fixed T0 = 300 K and 兩⌬兩 = 0.5. Here N changes from 20 to 100.
room temperature rectification is only 2% with 兩⌬兩 ⬇ 0.05.
However, the rectification ratio is 10% for uniform massed
nanocone and 12% for graded massed nanocone with the
same ⌬ value. With graded mass distribution, the rectifica-
tion ratio increases with 2%, which agrees well with the
experimental results in Ref. 8. At small temperature differ-
ence range, the geometric impact is more effective than the
mass impact. Also the rectification ratio of nanocone is also
much higher than that of CNT 共n , 0兲 / 共2n , 0兲 junction. At
room temperature and with 兩⌬兩 = 0.5, the rectification of
nanocone is 96%, while that of CNT intramolecular junction
is only about 15%.9 Our results demonstrate that carbon
nanocone rectifier has obvious advantage over CNT based
thermal rectifiers,8,9 and no additional mass loading process
is required in the fabrication of nanocone thermal rectifier.
The rectification versus temperature T0 is shown in Fig.
3共a兲. As the temperature increases, the heat fluxes increase,
and the increase in J− is higher than the increase in J+
关see Fig. 3共b兲兴, which leads to the reduction in the rectifica-
tion ratio. It demonstrates that nanocone has a significant
rectification effect in a wide temperature range. Here the
temperature 共TMD兲 range is from 200 to 400 K. Based on the
results of quantum modification to TMD in Ref. 21, the results
presented here correspond to real temperature range of 120–
360 K, which are experimentally observable.
In the following, we explore the impact of length on the
rectification with the longest nanocone side face length of
around 14 nm 共N = 100兲. Figure 3共c兲 shows that the rectifica-
tion is independent of the length. As shown in Fig. 3共d兲, the
heat fluxes are independent of the size, which means that
energy transports ballistically in the system. In the molecular
junction typed CNT thermal rectifier,9 the rectification de-
creases quickly when the device length is increased because
the role of the interface is suppressed in a large system.
However, in the nanocone rectifier proposed here, high rec-
tification can be achieved in the practical nanocone length
scale and adds the feasibility of constructing thermal rectifier
with carbon nanocones.
To understand the underlying mechanism of the rectifi-
cation phenomenon, we calculate the power spectra. The
power spectrum is a good way to explain the heat rectifica-
tion effect both qualitatively and quantitatively.26 It is calcu-
lated from the Fourier transform of the velocity. We show the
243111-3 Yang, Zhang, and Li
FIG. 4. 共Color online兲 Power spectra of atoms at the 4th 共close to the top,
solid lines兲 and 37th 共close to the bottom, dashed lines兲 atomic layers.
The heat baths are contacted with 2nd and 39th layers, respectively. 共a兲
T0 = 300 K, ⌬ = 0.5; 共b兲 T0 = 300 K, ⌬ = −0.5. It corresponds to big heat flux
when ⌬ ⬎ 0 and corresponds to small heat flux with ⌬ ⬍ 0.
power spectra of atoms close to the top and the bottom 共4th
and 37th layers, respectively兲 in Fig. 4. The frequency range
is from 0 to 60 THz, which is consistent with the reported
vibration spectra15,27–29 of CNTs. In bulk materials, the opti-
cal modes contribute little to heat flux. However, in nano-
scale system such as CNT, anomalous thermal conductivity
was observed, which did not obey the Fourier law.30 In the
non-Fourier system, optical phonon 共high frequency兲 also
plays a major role in the heat flux.27 As shown in Fig. 4共a兲,
⌬ ⬎ 0, the power spectra of the top and bottom atomic layers
overlap perfectly in a large frequency range, which means
the phonon can easily go through the nanocone along the
direction of temperature gradient and correspond to large J+.
On the contrary, when ⌬ ⬍ 0 关Fig. 4共b兲兴, there is an obvious
mismatch in the power spectra both in low and high fre-
quency bands. The large mismatch shows the weak correla-
tion between the two ends. As a result, the phonon is difficult
to go through the structure and thus leads to very small J−.
The match/mismatch of the power spectra between the bot-
tom and top layers results in the rectification phenomenon. In
order to quantify the above analysis, the overlaps 共S兲 of the
power spectra of the two layers are calculated as26
冕
Pb共␻兲Pt共␻兲d␻
冕 冕
S⫾ = . 8, 61 共2004兲.
Pb共␻兲d␻ Pt共␻兲d␻
Here S⫾ corresponds to the case of ⌬ ⬎ 0 and ⌬ ⬍ 0,
respectively, Pt共␻兲 is the power spectrum of the top layer,
and Pb共␻兲 is the power spectrum of the bottom layer. From
Fig. 4, a S+ / S− ratio of 1.2 is observed, which corresponds to
larger power spectra overlap when ⌬ ⬎ 0. This picture indeed
illustrates that the heat flux and rectification phenomena cor-
relate strongly with the overlap of the power spectra of the
two ends.
In conclusion, we have demonstrated an excellent ther-
mal rectifier from carbon nanocone. Obvious thermal rectifi-
cation ratio in a large temperature range from 200 to 400 K
Appl. Phys. Lett. 93, 243111 共2008兲
has been observed. It shows that the graded geometric asym-
metry is of remarkable benefit to increase the rectification
ratio. Compared to the quick decrease in rectification ratio
with device length in CNT rectifier, the weak dependence of
rectification ratio on nanocone length is of particular impor-
tance for phononics application. In nanocone, the heat flux is
controlled by match/mismatch of the power spectra between
the top and bottom atomic layers. In contrast to the previous
studies of thermal rectifiers which have three1 or two coupled
segments,2,3 the nanocone can control the heat current by
itself. More importantly, in nanocone we do not need any
on-site potential required in previous theoretical models,1–3
which is hard to control experimentally, and moreover, the
onsite 共substrate兲 potential generally reduces the heat current
significantly. These advantages of carbon nanocone thermal
rectifier raise the exciting prospect that the practical phonon-
ics device can be realized with a full-carbon system.
This work was supported in part by an ARF grant,
R-144-000-203-112, from the Ministry of Education of the
Republic of Singapore and Grant R-144-000-222-646 from
the National University of Singapore.
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