Adjustable magnetoresistance in semiconducting carbonized phthalonitrile resin

Article abstract of DOI:10.1039/d1cc04300e

Herein, we report the first example of controllable magnetoresistance in a semiconducting carbonized phthalonitrile resin. This special phenomenon is explained using the different ratios of graphite-like (sp2) and diamond-like (sp3) bonds and localization

Full text of DOI:10.1039/d1cc04300e

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Adjustable magnetoresistance in semiconducting carbonized
phthalonitrile resin†
Received 00th January 20xx,
Accepted 00th January 20xx
a
e
a,d
e
,a
f
f
Chong Gao, Ming Yang, Wenhao Xie, Hang Zhang, Hongbo Gu,* Ai Du, Zhong Shi, Ying
b
,b
,c
DOI: 10.1039/x0xx00000x
Guo, Heng Zhou,* Zhanhu Guo*
Herein, we first reported a controllable magnetoresistance in the arising from the spin-dependent scattering. Recently,
semiconducting amorphous carbon has aroused research
interest in the MR field because of its variable band gaps
semiconducting carbonized phthalonitrile resin. This special
phenomenon is interpreted by the different ratios of graphite-
originating from its symmetry hybridization as well as tuneable
2
3
like (sp ) and diamond-like (sp ) bonds and localization length
a ) as well as the density of states at the Fermi-level (N(E )).
7
electrical and optical properties. It’s reported that the
2
(
0
F
amorphous carbon3 including graphite-like (C(sp )) and
diamond-like (C(sp )) bonds could be formed in the process of
8
The magnetoresistance (MR) effect refers to the resistance polymer carbonization. Especially, the amorphous carbon
1
change of a material under the external magnetic field, which would exhibit the complex electrical and magnetic properties
2
3
has been applied in the high-density information storage, hard owing to the different ratios of C(sp ) to C(sp ) and its complex
2
9
disk drives, and magnetic recording devices. In the last decade, microstructures. As a consequence, the manipulation of ratio
2
3
the carbon-based materials (such as graphene and carbon between C(sp ) and C(sp ) bonds might alter the MR effect in
1
0
nanotubes), as a kind of promising electronic materials, have the amorphous carbon.
attracted considerable attention in the MR device due to their
As a high-performance thermosetting resin, phthalonitrile (PN)
resin has great potential applications in aerospace, navigation,
microelectronics, and other industrial fields
light weight, good chemical stability, weak spin-orbit coupling
3
4
and hyperfine interaction. For example, Takuya et al.
1
1-13
due to its
systematically investigated the room-temperature negative MR
in the defective graphene and found that the hopping
conduction was a suitable transport mechanism for explaining
the obvious change in resistance relying on the direction of the
excellent thermal stability, mechanical property, superior
1
3
radiation resistance, and low moisture absorptivity. Generally,
the curing process of PN resin is a nucleophilic addition
1
4
5
reaction, in which the cyano group on the PN monomer tends
to transform into three main structures, namely phthalocyanine,
triazine, and isoindoline under the action of relevant catalysts.
Owing to the existence of high-temperature resistant triazine
and phthalocyanine structures, PN resin displays a superior
thermal stability and high carbon char yield in the inert
atmosphere, which is favourable to form the amorphous
external magnetic field. Reza et al. also reported the negative
MR effect with a value of -9.0% at the temperature of 5 K in
the carbon nanotube yarns for a magnetic field of 5 T, which
depended on the weak spin-orbit effect. The interference effect
was intensified as the magnetic field was increased, which
could increase the long-distance hopping probability of charge
carrier, leading to a low resistance in these carbon nanotube
1
5
6
carbon. After carbonization, a lot of polycondensed rings
might be constructed in the cross-linked structures of PN resin,
which might build up a transport pathway for the charge
carriers hopping or tunnelling through the mixed-valence
interactions of the molecular orbitals and provide a tunable
electrical conductivity to the carbonized PN resin as a function
yarns. Zhu et al. found an adjustable MR effect in the
polyacrylonitrile-based carbon nanocomposite fiber that was
fabricated by electrospinning and high temperature annealing,
a.
1
6
Shanghai Key Lab of Chemical Assessment and Sustainability, School of Chemical
of annealing temperature and annealing time. However, the
charge transport mechanism and MR effect in the carbonized
PN resin have not been investigated so far.
Science and Engineering, Tongji University, Shanghai 200092, China. E-mail:
hongbogu2014@tongji.edu.cn
Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. E-
b.
mail: zhouheng@iccas.ac.cn
Integrated Composites Lab (ICL), Department of Chemical & Biomolecular
Engineering University of Tennessee, Knoxville, TN, 37966, USA. E-mail:
zguo10@utk.edu
Key Laboratory of Materials Processing and Mold (Zhengzhou University),
Ministry of Education, National Engineering Research Center for Advanced
Polymer Processing Technology, Zhengzhou University, Zhengzhou, China
Institute of Engineering Thermophysics, Chinese Academy of Sciences, Beijing
c.
In this work, we firstly report a tunable MR phenomenon in the
carbonized fluorine-containing phthalonitrile resin (as depicted
in scanning electron microscope (SEM, Hitachi S-4800 system)
image of Fig. S2) that has been fabricated by cross-linking of
d.
2,2-bis[4-(3,4-dicyano-phenoxy)phenyl]
hexafluoro-propane
e.
(FPN) monomer under the presence of 4-(4-aminophenoxy)
phthalonitrile (APN) catalyst (which is called FPN/APN resin).
The X-ray diffraction (XRD, D8 Advance X-ray powder
diffractometer) results confirm that there is a certain part of
crystalline graphite-like structures in these carbonized
1
00049, China
f.
Shanghai Key Laboratory of Special Artificial Microstructure Materials and
Technology, School of Physics Science and Engineering, Tongji University,
Shanghai 200092, China
†
Electronic Supplementary Information (ESI) available. See DOI:
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o
FPN/APN resins since the diffraction peaks at 2 = 25 and 44
conditions on the MR effect in the carbonized FPNVie/wAAPrtNiclerOensliinne,
in
Fig. 1A. Most condition and MR performance. The MR performance for 6%
DOI: 10.1039/D1CC04300E
are connected with the (0 0 2) and (1 0 0) crystallographic we have addressed the relationship between the anneal g
1
7-19
planes of hexagonal graphite-like carbon,
importantly, we have found that these carbonized FPN/APN weight percentage of FPN/APN resin annealed at temperatures
o
resins exhibit semiconducting properties and its MR effect of 600, 700 and 800 C is evaluated, as demonstrated in Fig.
could be easily controlled by the annealing temperature (e.g. - 1B(b, d, e). As laid out in Fig. 1B, the MR value of 6FPN-600
o
8
6
1
.7% and 3.6% for annealing temperature of 800 and 600 C at and 6FPN-700 is 3.6% and 0.4% at magnetic field of 9 T,
wt% of APN, respectively) and amounts of APN catalyst (e.g. respectively, while that of 6FPN-800 is -8.7%. These results
.7% and -0.1% for 3 and 10% weight percentage of APN at express that the annealing temperature could affect the MR
annealing temperature of 800 C, accordingly). Afterwards, we effect of carbonized FPN/APN resin. With the increase of
have elucidated this phenomenon by the different ratios of C(sp ) annealing temperature from 600 to 800 C, the MR of
to C(sp ) bonds through X-ray photoelectron spectroscopy (XPS, carbonized FPN/APN resin is changed from positive (3.6% for
Kratos AXIS Ultra DLD spectrometer) and C solid-state nuclear 600 C) to negative (-8.7% for 800 C). In contrast, after
magnetic resonance ( C-NMR, Bruker Avance III), and localization prolongation of annealing time to 40 min, the 6FPN-800-40
o
2
o
3
1
3
o
o
1
3
length (a ) as well as the density of states at the Fermi-level (N(E )) sample does not exhibit obvious MR property (only 1.1%), Fig.
0
F
obtained from wave function shrinkage model and forward 1B(f). In fact, the unpaired electrons (or spins) play an
2, 16
interference model. In the experiment, the FPN was firstly important role in the MR effect.
It’s reported that during the
fabricated by a modified Keller’s method. Please see details in annealing, more and more unpaired electrons are formed and
ESI†
. Then, the FPN/APN resin was prepared according to the eventually reach a certain concentration level in the PN resin,
2
0
which is beneficial for producing MR effect. However, after
annealing at 800 C for a long time, the 6FPN-800-40 sample
may possess more stable and ordered structures, leading to the
reduce of unpaired electrons (or spins) and weak MR effect.
literature report. In brief, the mixed FPN/APN blends were
put into a three-neck round-bottom flask and magnetically
o
o
stirred at 160 C for 5 min. After that, the melting mixture was
poured into the silicone mould and placed in an oven with the
curing sequences of 200 C for 4 h, 250 C for 4 h, 280 C for 6
h, and 300 C for 6 h to attain the FPN/APN resin (please see
o
o
o
o
curing mechanism in Scheme S1). In addition, we have utilized
different weight percentages of APN (the weight percentage
was 3, 6, and 10%, accordingly) to manufacture the FPN/APN
resin for comparison. Finally, the FPN/APN resins were placed
in a tube furnace (GSL-1100X-S, Kejing Co., Ltd, Hefei,
o
China) at 550 C for 8 h followed by processing in an infrared
furnace (Beijing Huace Testing Instrument Co., Ltd.) with the
o
o
heating sequences of 600 C for 20 min, 700 C for 20 min, and
8
o
00 C for 20 min to obtain the carbonized FPN/APN resin.
The FPN/APN resins with 3, 6, and 10% weight percentage of
o
APN calcinated at 800 C for 20 min were named as 3FPN-800,
6
FPN-800, and 10FPN-800, respectively. And the FPN resin
o
with 6% weight percentage of APN annealed at 600 C for 20
o
o
min, 700 C for 20 min and 800 C for 40 min was indexed as
FPN-600, 6FPN-700, and 6FPN-800-40, separately
6
.
1
3
Fig. 2 High resolution C 1s XPS spectra and C-NMR spectra
for (A) and (C) 6FPN-600; (B) and (D) 6FPN-800.
Since the MR property in the amorphous carbon might be
2
3
linked with the ratio of C(sp ) and C(sp ) bonds as mentioned
1
3
above, the XPS and C-NMR measurements are firstly
2
3
conducted to evaluate the ratios of C(sp ) and C(sp ) bonds in
the carbonized FPN/APN resins. The high resolution C 1s XPS
spectra of 6FPN-600 and 6FPN-800 are drawn in Fig. 2A and
B. Due to the presence of heteroatoms in the system, four
characteristic peaks are deconvoluted. It’s reported that the area
ratio of peaks at ~284.6 and ~285.6 eV is attributed to the ratio
Fig. 1 (A) XRD pattern of 6FPN-800; and (B) room
temperature magnetoresistance for (a) 3FPN-800, (b) 6FPN-
8
6
00, (c) 10FPN-800, (d) 6FPN-600, (e) 6FPN-700, and (f)
FPN-800-40.
2
3
21
of C(sp ) and C(sp ) clusters. Generally, the carbon material
2
It’s noticed that the absolute MR values for the as-prepared contained dominant sp hybrid carbon denotes a greater
2
carbonized FPN/APN resin displayed in Fig. 1B manifest the electrical conductivity, since the threefold coordinated C(sp )
obvious magnetic field dependent property and increase with could provide a free electron that does not exist in the fourfold
3
22
increasing magnetic field. Interestingly, the 6FPN-800 coordinated C(sp ). It’s worthy noting that the ratio of
2
3
illustrates a negative MR effect with the highest MR value of - C(sp )/C(sp ) is increased from 0.57 for 6FPN-600 to 1.19 for
.7% at magnetic field of 9 T, Fig. 1B(b), whereas other 6FPN-800 with increasing the annealing temperature,
samples like 3FPN-800, 6FPN-600, 6FPN-700 and 6FPN-800- suggesting an increased electrical conductivity and decreased
8
2
3
4
3
1
0 reveal a positive MR effect with the highest MR value of 1.7, resistivity for 6FPN-800. The changed ratio of C(sp )/C(sp )
.6, 0.4, and 1.1% at magnetic field of 9 T, respectively, Fig. under the different annealing temperatures alters the transport
B(a, d, e, f). Moreover, the 10FPN-800 sample has no of charge carriers in the carbonized FPN/APN resins under the
significant MR effect with a calculated MR value of around 0, magnetic field. This might be one reason for the changeable
Fig. 1B(c). With the aim to explore the effect of annealing MR effect in the 6FPN-600 (3.6%) and 6FPN-800 (-8.7%). Fig.
2
| Chem. Commun., 2021, 00, 1-3
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1
3
2
6
C and D presents the C-NMR spectra of 6FPN-600 and measurement when the temperature is lower than 1V3ie0w AKrt.icTle hOanltin’se
FPN-800. It’s found that two distinct peaks are observed at the reason that there is no data below 13
DOI: 10.1039/D C04300E
0 K. The va1Clue of T
0
1
3
5
chemical shift of ~120 ppm and ~15 ppm in the C-NMR for 6FPN-800 is 4.78×10 K, which is decreased as the ratio of
spectra of these two samples, corresponding to the C(sp ) and C(sp )/C(sp ) is increased from 0.57 for 6FPN-600 to 1.19 for
C(sp ) characters, respectively. The predominantly difference 6FPN-800. That’s the reason that the electrical conductivity of
in the C-NMR spectra between 6FPN-600 and 6FPN-800 is 6FPN-800 is higher than that of 6FPN-600. The TAT model is
the intensity ratio of these two peaks that is related to the sp
and sp hybridized carbon characters, in which the peak eqn (S3). The E (activation energy) and R (a constant) could be
intensity ratio of sp to sp hybridized carbon belonged to the obtained from the slope and intercept of the linear fit plot of ln
FPN-600 (9.18) is lower than that for 6FPN-800 (13.72). This (R) ~ T (Fig. 3D). The relevant fitting results for 6FPN-600,
2
2
3
3
23
1
3
2
accepted in the temperature range from 180-290 K as shown in
3
0
2
3
-
1
6
result is consistent with the XPS result.
6FPN-700, and 6FPN-800 are described in Fig. 3D and Table
S1. The activation energy E computed from the slope of linear
fit plot of ln (R) ~ T (Fig. 3D) for 6FPN-600, 6FPN-700, and
2
Owing to the presence of C(sp ) clusters (as conductors) and
-1
3
C(sp ) clusters (as insulators) in the amorphous carbon, the
electrical transport property of charge carriers in the amorphous
carbon is alike to the hopping or tunnelling conduction in the
6FPN-800 resins is 140.30, 77.20 and 32.41 meV, respectively,
and decreases with increasing annealing temperature. The lower
E for the charge carrier’s hopping could lead to a higher
2
4
disordered semiconducting system. With the purpose of
further figuring out the relationship between MR effect and
electrical transport of charge carriers in these carbonized
FPN/APN resins, we have introduced the Mott variable range
hopping (VRH) model and thermally activated transport (TAT)
model to study their electrical transport mechanism. Firstly, we
have explored the temperature dependent resistivity property of
these carbonized FPN/APN resins. Fig. 3A&B describe the
changes of resistivity in the temperature range of 100-290 K for
29, 30
electrical conductivity of materials.
This is in agreement
with the results acquired above. Hence, the Mott VRH model
and TAT model are the possible suitable mechanisms for
explaining the resistivity and temperature relationship for all
the carbonized FPN/APN systems.
6
FPN-600, 6FPN-700, and 6FPN-800, respectively. It’s noticed
that these three samples reveal a low resistivity after annealing
421.62, 10.32 and 0.19  cm at room temperature for 6FPN-
00, 6FPN-700, and 6FPN-800, respectively), which may be
associated with the building and ordering of polycondensed
(
6
1
6
rings in the FPN/APN resin during the annealing process (the
regular FPN/APN resin is insulating.). In order to understand
this charge transfer and low resistivity, we have exploited First-
principle calculations and finite temperature molecular
dynamics (FTMD) simulations to simulate the possible final
structures of carbonized FPN/APN resin, Fig. S5-S7. The
possible formed continuous conjugation structures from
polyphthalocyanine and polytriazine structures after annealing
may supply the charge carrier transfer pathway and contribute
to this low resistivity. The proposed charge carrier transfer
mechanism is laid out in Fig. S8. It is also observed that the
resistivity in these three samples is reduced with the increasing
Fig. 3 Resistivity vs. temperature for (A) 6FPN-600, (B) (b)
-1/4
6
FPN-800, and (e) 6FPN-700; (C) ln(σ) ~ T curves from 100
2
5,
temperature, representing a typical semiconducting property.
-1
to 180 K, and (D) ln(R) ~ T curves plotted from 180 to 290 K
2
6
Afterwards, we have exploited Mott VRH model and TAT
model to evaluate this charge carrier transport mechanism
for (b) 6FPN-800, (d) 6FPN-600, and (e) 6FPN-700.
theoretically in two different temperature ranges. Normally, the It’s reported that the MR effect might be connected with the
7
Mott VRH model is always used at a lower temperature range degree of disorder in the disordered semiconducting system. In
2
7
relative to the TAT model.
this work, we have applied Raman analysis to determine the
degree of disorder since the full width at half maximum
In this work, after fitting with the Mott VRH model by eqn (S2),
the 3D Mott VRH model is more suitable for these carbon
-1
(
FWHM) in the D-band (~1350 cm , conforms to the defects in
the carbon system) is correlated with the degree of disorder in
-
1/4
systems, and the linear plot of the ln ( ~ T within the 180-
90 K is drawn in Fig. 3C. The T0 (Mott characteristic
31
system. Fig. 4A provides the Raman spectra of 6FPN-600,
2
6FPN-700, and 6FPN-800. The value of FWHM for 6FPN-600,
-
1
temperature) and  (a constant representing the conductivity of
0
6FPN-700, and 6FPN-800 is 266.32, 254.12, and 201.04 cm ,
respectively. Consequently, the 6FPN-800 possesses the lowest
degree of disorder among these three samples and the degree of
disorder has a huge decrease for 6FPN-800 relative to 6FPN-
600 and 6FPN-700. For 6FPN-600 and 6FPN-700, the positive
MR is declined with the degree of disorder. As for 6FPN-800,
the MR value is changed to negative and the degree of disorder
is significantly decreased. In the Mott VRH model, the wave
function shrinkage model (eqn (S4)) and forward interference
model (eqn (S10)) are adopted to interpret the positive MR
the sample at the infinite high temperature) are calculated
through the linear fit of this linear plot, corresponding to the
slope and intercept, separately. These results are outlined in
Table S1. From Table S1, it’s seen that both T and  of
0
0
carbonized FPN/APN resins are decreased apparently as the
processing temperature increases. Usually, the value of T0
corresponds to the charge carrier scattering, and the higher the
value of T , the higher energy required for the charge carrier’s
0
2
8
hopping. Consequently, the 6FPN-800 sample signifies the
3
2
highest electrical conductivity, as shown in Fig. 3B. The value
effect and negative effect, accordingly, for attaining their
8
of T for the 6FPN-600 is as high as 2.74×10 K, which makes
0
localization parameters including localization length (a , eqns
0
its resistivity value exceeds the upper limit of the instrument
(
S6&S8)), hopping length (Rhop, eqn (S11)), and the density of
This journal is chemical commnucations © The Royal Society of Chemistry 2021
Chem. Commun., 2021, 00, 1-3 | 3
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states at the Fermi level (N(E ), eqn (S12)). The calculated a0 5. R. Ghanbari, S. R. Ghorbani, H. Arabi and J. FoVrioewugAhrtiic,leSOynnltinhe.
F
for 6FPN-600, 6FPN-700, and 6FPN-800 is 3.13. 2.86, and
Met., 2018, 242, 55-60.
DOI: 10.1039/D1CC04300E
8
6
1
.23 nm at magnetic field of 9 T, respectively. The Rhop for 6. J. Zhu, M. Chen, H. Qu, H. Wei, J. Guo, Z. Luo, N.
FPN-600, 6FPN-700, and 6FPN-800 is 36.54, 18.63, and
Haldolaarachchige, D. P. Young, S. Wei and Z. Guo, J. Mater.
Chem. C, 2014, 2, 715-722.
7.49 nm, accordingly. The N(E ) for 6FPN-600, 6FPN-700,
F
3
4
35
36
3 -1
and 6FPN-800 is 6.61×10 , 8.96×10 , and 2.07×10 (J cm ) , 7. A. S. Saleemi, R. Singh, W. Sun, Z. Luo and X. Zhang, Carbon,
separately, as shown in Fig. 4B. This means that with the MR 2017, 122, 122-127.
value is changed from positive to negative (MR value of 6FPN- 8. S.-Y. Son, M. Park, D. S. Lee, S. Lee, J. Han, G. Y. Jung and H.-
00, 6FPN-700 and 6FPN-700 is 3.6, 0.4, and -8.7%, I. Joh, Carbon, 2019, 142, 285-290.
respectively) and the ratio of C(sp )/C(sp ) is increased from 9. M. Du, M. Yao, J. Dong, P. Ge, Q. Dong, E. Kovats, S. Pekker,
6
2
3
0
.57 for 6FPN-600 to 1.19 for 6FPN-800, the a is decreased
S. Chen, R. Liu, B. Liu, T. Cui, B. Sundqvist and B. Liu, Adv.
Mater., 2018, 30, 1706916.
0
first and then increased, whereas the Rhop is continuously
decreased and N(E ) is always raised. The increment of N(E ) 10. A. S. Saleemi, R. Singh, Z. Luo and X. Zhang, Diamond and
F
F
under the magnetic field is much higher than that of Rhop,
leading to the transition of MR from positive to negative.
Relat. Mater., 2017, 72, 108-113.
11. X. Yang, W. W. Lei, Q. C. Liu, Y. Li, K. Li, P. Wang and W.
Feng, Compos. Commun., 2021, 26, 100791.
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3
1
1
1
2. Z. Weng, K. Zhang, Y. Qi, T. Zhang, M. Xia, F. Hu, S. Zhang,
C. Liu, J. Wang and X. Jian, Carbon, 2020, 159, 495-503.
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Fig. 4 (A) Raman spectra as well as (B) MR as a function of
N(E ) and a at magnetic field of 9 T for (d) 6FPN-600, (e)
F
0
2
569-2576.
6FPN-700, and (b) 6FPN-800.
7. G. Wu, Y. Hu, Y. Liu, J. J. Zhao, X. L. Chen, V. Whoehling, C.
Plesse, G. T. M. Nguyen, F. Vidal and W. Chen, Nat. Commun.,
In summary, the semiconducting carbonized FPN/APN resin
system with an adjustable MR effect has been fabricated by the
high temperature annealing of FPN/APN resins. Their room-
2
015, 6, 7258.
1
1
2
2
2
8. Y. Wang, W. Xie, H. Liu and H. Gu, Adv. Compos. Hybrid
Mater., 2020, 3, 473-484.
9. S. O. Mirabootalebi, Adv. Compos. Hybrid Mater., 2020, 3, 336-
temperature MR effect is changed from 3.6% and 0.4% to -
o
8
.7% for annealing at temperatures of 600, 700, and 800 C
3
43.
with 20 min at a magnetic field of 9 T, respectively. The Mott
VRH model and TAT model elucidate a 3D VRH electrical
transport mechanism in these carbonized FPN/APN resins and
the related E is 140.30, 77.20 and 32.41 meV for 6FPN-600,
0. C. Gao, H. Gu, A. Du, H. Zhou, D. Pan, N. Naik and Z. Guo,
Polymer, 2021, 219, 123533.
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P. Young, J. Lin and Z. Guo, Mater. Today Phys., 2021, DOI:
6
FPN-700, and 6FPN-800, respectively. With the ratio of
2
3
C(sp )/C(sp ) is increased from 0.57 for 6FPN-600 to 1.19 for
FPN-800, the a is decreased from 3.13 to 2.86 nm and then
6
0
1
0.1016/j.mtphys.2021.100502.
increased to 8.23 nm. Moreover, the increment of N(E ) under
F
2
2
2
2
2
3. K. J. Harris, Z. E. M. Reeve, D. N. Wang, X. F. Li, X. L. Sun
and G. R. Goward, Chem. Mater., 2015, 27, 3299-3305.
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the magnetic field is much higher that of Rhop. These results
lead to the MR transition from positive to negative for these
carbonized FPN/APN resins.
2
019, 148, 512-517.
The authors are grateful for the support and funding from the
Foundation of National Natural Science Foundation of China
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Young, J. F. Zhu and Z. H. Guo, Adv. Compos. Hybrid Mater.,
(
1
No. 51703165, 51888103), Shanghai Rising-Star Program (No.
9QA1409400). This work is supported by Shanghai Science
and Technology Commission (14DZ2261100).
Conflicts of interest
2
021, DOI: 10.1007/s42114-021-00242-z.
There are no conflicts to declare.
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