Article

Cite This: ACS Nano 2019, 13, 1547−1554 www.acsnano.org

A Paper-Like Inorganic Thermal Interface

Material Composed of Hierarchically
Structured Graphene/Silicon Carbide
Nanorods
Wen Dai,†,∥,¶ Le Lv,†,¶ Jibao Lu,*,‡ Hao Hou,† Qingwei Yan,† Fakhr E. Alam,†,∥ Yifan Li,§
Xiaoliang Zeng,‡ Jinhong Yu,†,∥ Qiuping Wei,⊥ Xiangfan Xu,# Jianbo Wu,∇ Nan Jiang,*,†,∥
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Shiyu Du,§ Rong Sun,‡ Jianbin Xu,○ Ching-Ping Wong,◆ and Cheng-Te Lin*,†,∥
†
Key Laboratory of Marine Materials and Related Technologies, Zhejiang Key Laboratory of Marine Materials and Protective Technologies, Ningbo Institute of
Materials Technology and Engineering (NIMTE), ‡Shenzhen Institutes of Advanced Technology, and §Ningbo Institute of Materials Technology and
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Engineering (NIMTE), Chinese Academy of Sciences, Ningbo 315201, PR China

∥
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, PR China
⊥
State Key Laboratory of Powder Metallurgy, School of Materials Science and Engineering, Central South University, Changsha 410083, PR China
#
Center for Phononics and Thermal Energy Science School of Physics Science and Engineering, Tongji University, Shanghai 200092, China
∇
State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai, 200240, PR China
○
Department of Electronics Engineering, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong 999077, China
◆
School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States

*
S Supporting Information

ABSTRACT: With the increasing integration of devices in electronics

fabrication, there are growing demands for thermal interface materials
(TIMs) with high through-plane thermal conductivity for efficiently
solving thermal management issues. Graphene-based papers consisting of
a layer-by-layer stacked architecture have been commercially used as
lateral heat spreaders; however, they lack in-depth studies on their TIM
applications due to the low through-plane thermal conductivity (<6 W
m−1 K−1). In this study, a graphene hybrid paper (GHP) was fabricated by
the intercalation of silicon source and the in situ growth of SiC nanorods
between graphene sheets based on the carbothermal reduction reaction.
Due to the formation of covalent C−Si bonding at the graphene−SiC
interface, the GHP possesses a superior through-plane thermal conductivity of 10.9 W m−1 K−1 and can be up to 17.6 W m−1 K−1 under
packaging conditions at 75 psi. Compared with the current graphene-based papers, our GHP has the highest through-plane thermal
conductivity value. In the TIM performance test, the cooling efficiency of the GHP achieves significant improvement compared to that of
state-of-the-art thermal pads. Our GHP with characteristic structure is of great promise as an inorganic TIM for the highly efficient
removal of heat from electronic devices.
KEYWORDS: graphene hybrid paper, silicon carbide nanorods, hierarchical structure, through-plane thermal conductivity,
thermal interface materials

fficient heat dissipation is of crucial importance for high-

E power and high-frequency electronic devices to avoid

working under overheating conditions, which are
harmful to the device service life and reliability.1 In actuality,
this problem, thermal interface materials (TIMs) are commonly
applied to fill these microgaps and bridge between the heat
source and the heat sink for removing excess heat from the
devices.4 Conventional TIMs are made of polymer-based
composites filled with thermally conductive materials, such as
microgaps between the mating surfaces of heat-generating
electronic components and the heat sink are full of air, which is a
very poor heat conductor with ultralow thermal conductivity (κ: Received: September 26, 2018
≈ 0.032 W m−1 K−1),2 leading to a high thermal interface Accepted: February 6, 2019
resistance for the suppression of thermal percolation.3 To solve Published: February 6, 2019

© 2019 American Chemical Society 1547 DOI: 10.1021/acsnano.8b07337

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Figure 1. Surface morphologies of (a) pristine and (b) SiO2 NPs-decorated GO in TEM. The corresponding (c) SEM image and (d) EDS
spectrum of panel b. (e) Schematic of the fabrication process and the photograph of GHP.

BN, AlN, Al2O3, etc., to achieve thermal conductivity values of decrease of through-plane heat-transfer capability. Drzal et al.
1−5 W m−1 K−1 (50−70 wt % filler content is required).5−7 applied a cold compaction process with 100 psi to graphene
However, with the rapid increase of integration density and paper and found that the through-plane thermal diffusivity
power consumption in electronics, the accompanying demand decreased by 60%.22 Therefore, so far, it is still lack of in-depth
for highly efficient heat dissipation is beyond the ability of studies on potential TIM applications based on paper-like
conventional TIMs with which to deal. Therefore, the graphene structure. As a result, to meet the requirement for use
development of TIMs with improved through-plane thermal as TIM, it is a major challenge to create a paper-like graphene
conductivity has become a subject of considerable scientific and structure with not only high through-plane thermal conductivity
technological interests. but also appropriate mechanical properties.
Graphene is a single layer of densely packed sp2-hybridized In this work, a graphene/SiC nanorod hybrid paper with
carbon atoms that exhibits a ultrahigh intrinsic thermal hierarchical structure was fabricated by vacuum filtration of a
conductivity of 3500−5300 W m−1 K−1 and large specific mixture of SiO2 nanoparticles (NPs)-decorated graphene sheets,
surface area of ∼2630 m2 g−1.8−10 Due to the above followed by high-frequency heat treatment to grow SiC
characteristics, graphene/polymer composites with enhanced nanorods between graphene layers. The through-plane thermal
thermal conductivity,11−13 graphene coatings for efficient diffusivity of as-prepared graphene hybrid paper (GHP) can be
radiative cooling,14 and graphene papers as heat spreaders15−17 improved by a factor of ∼2.2 compared to pristine paper.
have been extensively studied in recent years for development of Interestingly, under compression of 75 psi, the through-plane
the next generation of thermal management applications. thermal conductivity of GHP can be further increased up to 17.6
Among them, graphene papers composed of layer-by-layer W m−1 K−1, which significantly outperforms conventional
stacked graphene sheets have been commercially used as high- TIMs.4 The comparative tests between GHP and state-of-the-
performance heat spreaders in portable devices because of its art commercial TIMs also demonstrate the superior perform-
excellent in-plane thermal conductivity(κ: 1000−2000 W m−1 ance of GHP for cooling electronic devices.
K−1)18,19 and ease of mass production.20 Lian et al. fabricated a
graphene paper with the size of 18 in. × 4.5 in. and in-plane RESULTS AND DISCUSSION
thermal conductivity of 1434 W m−1 K−1 by integration of The hierarchically structured graphene/SiC nanorods was
electro-spray deposition and continuous roll-to-roll process.16 developed by the interaction of SiO2 NPs between graphene
However, in contrast to the superior in-plane thermal layers, followed by the growth of SiC nanorods by rapid heat
conductivity, conventional graphene paper exhibits a much- treatment at atmosphere. To act as the nucleation sites and
lower through-plane conductivity (κ: 0.1−3.4 W m−1 K−1)20−23 silicon sources, pristine graphene oxide (GO) was decorated
due to the high barrier for phonon transmission across a van der with SiO2 NPs through the hydrolysis of TEOS in an alkaline
Waals interface between graphene layers.20 Recently, some environment. The morphology of GO before and after SiO2 NPs
efforts have been done to solve this issue on improvement of the decoration is present in panels a−c of Figure 1, respectively, in
through-plane thermal conductivity of graphene papers. Jiang et which a uniform distribution of SiO2 NPs can be seen on the GO
al. constructed a graphene hybrid paper by growth of carbon surface after hydrolysis. The composition of SiO2 NPs-
nanoring between graphene sheets through annealing with the decorated GO was identified using energy-dispersive X-ray
assistance of metal catalysts.20 Although the through-plane spectroscopy (EDS) analysis in transmission electron micros-
thermal conductivity of the paper was improved by a factor of 3 copy (TEM), by which a strong Si peak can be found in Figure
after hybridization, the obtained value of 5.8 W m−1 K−1 is just 1d, and others peaks are assigned to the GO and copper grid,
close to that of commercial TIMs.4 Moreover, in the practical respectively.25 Figure 1e shows the schematic diagram of the
use, a proper packing pressure of 50−100 psi needs to be given fabrication process of GHP and also illustrates our concept of
to guarantee a good contact between TIMs and two mating this study to create a hierarchical microstructure composed of
surfaces.4 However, for the case of conventional graphene paper, graphene and SiC nanorods by a simple filtration and post-
the horizontally aligned graphene sheets would become more annealing process. As displayed in Figure 1e, a paper was first
ordered under normal compression, resulting in a further made by vacuum filtration of a mixture of the as prepared SiO2
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Figure 2. Top-view and cross-sectional SEM images of (a, c) GHP and (b, d) GP, respectively. The comparison of (e) XRD patterns, (f) Raman
spectra, (g) high-resolution XPS C 1s spectra, and (h) TGA curves between GHP and GP.

NPs-decorated GO and graphene sheets with the mass ratio of graphene sheets, other diffraction peaks at 35.8°, 60.2°, and
1:9 to obtain SiO2 NPs-intercalated paper-like structure. After 71.9° can be assigned to the (111), (220), and (311) crystal
filtration, a rapid annealing process was performed to grow SiC planes of 3C-SiC (JCPDS card no. 29-1129), respectively. A pair
nanorods between graphene layers at 1400 °C in air. The of tiny peaks can be seen at 28.6° and 47.3°, which may derive
formation of SiC nanorods is based on carbothermal reduction from the fully reduced silicon. Raman spectroscopy (Figure 2f)
reaction according to reactions 1−3,26 and the comparative indicates that the characteristic peaks of graphene can be found
XRD patterns and Raman spectra of the papers before and after at 1337 (D-band), 1556 (G-band), and 2685 cm−1 (2D-band),
annealing can be found in Figure S1: respectively.28 The evaluated I2D-to-IG ratio of 0.57 suggests the
SiO2(s) + 3C(s) = SiC(s) + 2CO(g) multilayer nature of graphene sheets. A pair of peaks at 772 and
(1) 906 cm−1 are in correspondence with the vibrational frequencies
SiO2(s) + CO(g) = SiO(g) + CO2(g) of transverse and longitudinal optical modes of 3C-SiC at the Γ
(2) point, respectively.29 The chemical composition of GHP and GP
3SiO(g) + CO(g) = SiC(s) + 2SiO2(l) was also analyzed by X-ray photoelectron spectroscopy (XPS),
(3)
as exhibited in Figures 2g and S5. In Figure 2g, the C1s peak of
According to the previous report, a relatively strong covalent GHP can be deconvoluted into four major components: C=C
bonding at the interface of graphene−SiC nanorods can be (44%, at 284.6 eV), C−O (13%, at 285.5 eV), C=O (6%, at
achieved.27 As a result, a GHP with the diameter of 40 mm and 286.3 eV), and C−Si (37%, at 283.3 eV), respectively.25,30 The
the thickness of 500 μm could be obtained. deconvolution of high-resolution Si2p signal in Figure S5b
The comparison of the microscopic morphologies of our reveals two peaks at 101.4 (Si−C, 95.7%) and 103.8 eV (Si−O,
GHP and graphene paper (GP) prepared with the same process 4.3%), respectively,25 indicating that the mass ratio of SiC
are presented in Figure 2a−d. In Figures 2a and S2a−c, with component in nanorods is ∼93.7 wt %. To investigate the mass
SiO2 NPs intercalation and post-annealing, the top surface of ratio of SiC nanorods in GHP, both GP and GHP were analyzed
GHP is fully covered by SiC nanorods with diameter of 20−100 by TGA in air, as in the curves shown in Figure 2h. Compared to
nm and the length of 5−15 μm, in contrast to the smooth top the complete decomposition of GP, the thermogravimetric
surface of GP (Figure 2b). TEM observations confirmed that the analysis (TGA) curve of GHP exhibits a residual weight of
crystalline 3C-SiC nanorods were synthesized with a [111] ∼6.94 wt % at 900 °C. In addition, the pure SiC nanorods were
preferred growth direction, and a thin amorphous SiO2 layer individually analyzed in the same conditions, showing a 1.3 wt %
(∼1 nm) can be seen on the outer surface of the nanorods (see weight increment at 900 °C. Accordingly, the mass ratio of SiC
Figures S3 and S4). Moreover, SiC nanorods are not only grown nanorods in GHP can be obtained to be ∼6.85 wt %, which is
on the surface but also act as the bridge between graphene layers composed of mainly crystalline SiC (∼6.42 wt %) and a small
within GHP to form a hierarchical structure, as shown in the amount of amorphous SiO2 (∼0.43 wt %), according to the
cross-sections in Figures 2c and S2d−f. The cross-sectional fitting results of Si2p XPS spectrum.
morphology of GHP is fundamentally different from that of GP To investigate the effect of the formation of hierarchical
(Figure 2d), which consisted of layer-by-layer stacking of structure within GHP on the thermal properties, thermal
graphene sheets and was in agreement with the microstructure diffusivity (α) of GHP and GP was measured by the laser flash
of conventional filtrated paper.18 method. The corresponding thermal conductivity (κ) can be
The crystal information and chemical composition of calculated by the equation:31 κ = α × ρ × Cp, where ρ is the
graphene papers with and without the hybridization of SiC sample density and Cp is the specific heat capacity (0.75 J g−1
nanorods are identified, as presented in Figure 2e−g. In Figure K−1; see Figure S6). As shown in Figure 3a, with the
2e, apart from the signal at 26.2° originated from (002) plane of development of graphene/SiC nanorod hybrid, the in-plane
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Figure 3. (a) In-plane and through-plane thermal diffusivities of GHP and GP. (b) The calculated thermal conductance at the graphene−SiC
nanorod interface bonded by covalent and van der Waals (vdW) interactions. (c) The test system configuration for determining the through-
plane heat-transfer capacity. (d) Surface temperature evolution and the (e) corresponding IR images of GHP and GP as a function of heating
time.

Figure 4. (a) Through-plane thermal properties of compressed GHP and compressed GP under 75 psi packing pressure. (b) Schematic
illustrating the difference of heat-flow across compressed GHP and compressed GP vertically. (c) Comparison of the through-plane thermal
conductivity of our GHP with the reported graphene-based papers. (d) Through-plane thermal conductivity as a function of environmental
temperature.

thermal diffusivity of GHP is ∼6% lower than that of GP. The the result of non-equilibrium molecular dynamics simulation
decrease is attributed to the formation of graphene/SiC (Figure 3b), the interfacial thermal conductance between
junctions on the graphene surface as scattering centers, which graphene/SiC nanorods connected by covalent C−Si bonding
hinder the phonon transport along the basal plane of graphene.20 (1.43 GW m−2 K−1) is 1 order of magnitude higher than vdW
In contrast, the through-plane thermal diffusivity of GHP (18.4 interactions (0.14 GW m−2 K−1) (details can be seen in Figure
mm2 s−1) is ∼2.2 times higher than that of GP (8.2 mm2 s−1). S7). The high interfacial thermal conductance at the covalently
Due to the fact that the spacing between graphene sheets was bonded interface using our proposed method is of significance to
expanded by the intercalation of SiC nanorods, the density of phonon transport across graphene and SiC nanorods.
GHP (0.8 g cm−3) is lower than that of GP (1.1 g cm−3). As a To compare the through-plane heat-transfer capacity between
result, the through-plane thermal conductivity of GHP (10.9 W GHP and GP, a pair of papers cut into the size of 10 mm × 10
m−1 K−1) shows a 60% enhancement compared to 6.8 W m−1 mm × 0.5 mm were placed on a ceramic heater (60 W) and kept
K−1 of GP (see Table S1). The more efficient heat-transfer at room temperature initially, followed by heating at the same
capacity of GHP along the through-plane direction is time (Figure 3c). The time dependence of their surface
contributed by both the intrinsic high thermal conductivity of temperature evolution on the heating time was recorded using
3C-SiC nanorods (bulk: 490 W m−1 K−1, nanorod: 76−88 W a thermocouple and calibrated infrared (IR) camera, respec-
m−1 K−1)32,33 and the creation of covalent C−Si bonding at the tively, as shown in panels d and e of Figure 3. We found that the
interface of graphene/SiC nanorods due to the in situ growth. As surface temperature of GHP increases faster than that of GP, and
Drzal et al. reported, the insertion of Au NPs into graphene always shows a higher value (e.g., ΔT = 27 °C at 300 s),
layers would lead to a reduction of through-plane thermal confirming the superior thermal conductivity of GHP along the
conductivity of graphene/Au NPs paper by 23%, owing to the through-plane direction.
weak interfacial heat conduction between them based on the The GHP composed of hierarchically structured graphene/
weak van der Waals (VdW) interaction.22 In our case, based on SiC nanorods has been demonstrated to exhibit a high through-
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Figure 5. (a) Schematic configuration of TIM performance evaluation system. Temperature evolution of ceramic heater as a function of (b)
heating time at the heater power of 30 W and (c) various applied powers after heating for 200 s. (d) The calculated heater temperature as a
function of effective thermal conductivity. (e) The comparison of heat dissipation capability based on simulated profiles.

plane thermal conductivity (up to 10.9 W m−1 K−1), by which dependence of through-plane thermal conductivity of GHP was
the GHP presents a great potential for TIM applications. investigated, and it shows a linear drop by 30% from 25 to 145
However, as the TIMs used in electronic packaging, generally, a °C in Figure 4d. Such behavior can be attributed the increased
packing pressure between 50−100 psi is required to guarantee relaxation time of phonons as the temperature increases and is in
good contact between the mating surfaces and TIMs to reasonable agreement with Umklapp scattering mechanism of
eliminate the microgaps at their interface.4 Therefore, the crystalline materials.35−37
change of through-plane thermal conductivity of GHP and GP Based on its high through-plane thermal conductivity, GHP
under vertical compression (75 psi) was studied. As revealed in may have the potential to act as a high-performance TIM to
Figure 4a, both of the samples show a lower thermal diffusivity of efficiently transfer heat across the heater−heat sink interface.
14.7 mm2 s−1 for compressed GHP and 4.8 mm2 s−1 for Therefore, a verification system for simulating heat dissipation
compressed GP, respectively, compared to that of pristine ones. process in electronic components was developed, as schemati-
This is because of the rearrangement of graphene sheets toward cally shown in Figure 5a. A state-of-the-art thermal pad (∼5 W
the horizontal direction during vertical compression (Figure m−1 K−1, 5000S35, Bergquist) was employed for comparison.
S8), leading to higher in-plane and lower through-plane thermal The GHP and 5000S35 with the size of 2 cm × 2 cm were
diffusivities of the resulting paper with an increase of thermal placed, respectively, between the ceramic heater and tge heat
anisotropy.16 Interestingly, we noticed that the reduction in sink with a same bond line thickness (BLT) of 250 μm and
thermal diffusivity of compressed GHP (19.7%) is lower than vertical pressure of 75 psi. A water-cooling system was attached
that of compressed GP (42.2%). This can be ascribed to the fact to keep the heat sink at room temperature, and the evolution of
that the SiC nanorods covalently bonded between graphene the heater temperature was recorded. In Figure 5b, after the
sheets lower the phonon diffusion barrier across the basal planes heater (30 W) turned on at 35 s, the heater temperature rise
of graphene (see Figure 4b), thus compensating for the decrease rapidly and then reached the equilibrium state. Obviously,
of through-plane heat conduction capability caused by the compared to the heater temperature without TIM, the cooling
rearrangement of graphene sheets. As a result, after applying the performance of GHP as TIM by a decrease of 18.3 °C at 200 s is
same vertical compression at 75 psi, the through-plane thermal much better than that of 5000S35 thermal pad (9.8 °C). The
conductivity of compressed GHP (17.6 W m−1 K−1) is more saturated temperatures of the heater versus applied power with
than 3 times higher than that of compressed GP (5.8 W m−1 and without TIMs are plotted in Figure 5c, in which the slope
K−1) under packaging conditions. values are 1.32 (without TIM), 0.99 (5000S35), and 0.72 °C
To the best of our knowledge, the GHP possesses the highest W−1 (GHP), respectively, indicating that GHP achieves 45.5%
through-plane thermal conductivity compared with the other and 27.3% improvements of cooling efficiency compared to the
graphene-based papers in the previous literature (see Figure 4c system without TIM and with 5000S35 thermal pad.
and Table S2)20−23,34 and also much better than that of A commercial computational fluid dynamics software
commercial TIMs, such as thermal gels, pads, and greases (up to (ANSYS Icepak) was then utilized for thermal analysis of our
4−5 W m−1 K−1).4 Besides, the environmental temperature test configuration at 30 W applied power (Figure S9), and the
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Figure 6. (a) Experimental setup and the schematic configuration for comparing the cooling efficiency between GHP and state-of-the-art
thermal pad based on desktop computer systems. (b) CPU core temperature evolution as a function of running time. (c) Comparative IR images
of the motherboard when 5000S535 and GHP were used as TIMs, respectively.

effective thermal conductivity (κeff) of two TIMs at the same CONCLUSIONS

measurement conditions can be estimated (see Figure 5d). In summary, a graphene/SiC nanorod hybrid paper was
Based on the values (κeff) for GHP (∼4.1 W m−1 K−1) and developed by a facile and easy to scale-up filtration method,
5000S35 (∼2.1 W m−1 K−1), not only superior through-plane followed by rapid heat treatment to grow in situ SiC nanorods
thermal conductivity, the calculated thermal contact resistance between graphene sheets based on carbothermal reduction
(two sides) of our GHP (47 K mm2 W−1) is also significantly reaction. The GHP shows a characteristic structure composed of
lower than that of 5000S35 thermal pad (69 K mm2 W−1). The hierarchical graphene/SiC nanorod architecture, leading to an
detailed calculation process can be found in Figure S10. The enhanced through-plane thermal conductivity (10.9 W m−1
lower thermal contact resistance can be attributed the K−1) by 60% compared to that of GP. In addition, conventional
characteristic hierarchical structure of graphene/SiC nanorods, graphene-based papers lose their through-plane thermal
which gives GHP not only a high through-plane thermal conductivity as a compressive force is vertically applied to
conductivity but also lower compressive modulus compared to them, which is not capable of developing practical TIM
that of 5000S35 (Figure S11). At 75 psi, the compressive applications. In contrast, due to the formation of relatively
modulus of GHP (∼0.64 MPa) is only about one-third of that of strong covalent C−Si bonding, the through-plane thermal
5000S35 (∼1.95 MPa). As a result, GHP with a soft conductivity of compressed GHP can be even higher (up to 17.6
compressibility is easier to fill up the microgaps between the W m−1 K−1) with a compression force of 75 psi. Accordingly, we
mating surfaces under packaging, leading to a maximum of demonstrated that the heater temperature of compressed GHP
by a decrease of 18.3 °C in TIM performance test is superior
contact area at the microscale and lower thermal contact
than 9.8 °C of commercial thermal pads (κ: 5 W m−1 K−1) with
resistance.38 Combining the high through-plane thermal
the cooling efficiency improving by 27.3%, which is also verified
conductivity and low thermal contact resistance, the simulated under actual operating conditions. By getting rid of the aging
temperature profiles in Figure 5e confirm the outstanding heat- issue of conventional polymer-based TIMs, our GHP with
transfer properties of our sample for TIM use. characteristically inorganic structure has great potential to be
A real TIM application for cooling computer CPU was carried used as high-performance TIMs with good thermal and
out to demonstrate superior heat dissipation performance of chemical stability.
GHP compared to 5000S35 thermal pad. In Figure 6a, GHP and
5000S35 with the same area and BLT were directly physically METHODS
fastened between the CPU (Intel Core i5-7500) and the
aluminum heat sink by vertically applying a packing pressure, Materials. Graphene sheets prepared by the intercalation and
exfoliation of graphite were supplied by Ningbo Morsh Technology
which was carried out using spring screws. The CPU is fixed on Co., Ltd., and the sample characterizations have been done in our
the motherboard, and the heat sink is connected to a cooling fan previous work.24 The lateral size and thickness of graphene sheets are
through the screws to transfer heat to the air flowing. A 5.4 ± 0.3 μm and 10.6 ± 0.3 nm, respectively. Graphene oxide (type
professional system diagnostics software (AIDA64)39 was HG03-1) with the typical lateral size and thickness of 3.0 μm and 2.5
employed to drive the CPU running at maximum heat- nm was supplied by Qingdao Huagaomoxi Technology Co., Ltd.
Tetraethoxysilane (TEOS), ammonia, and ethanol were purchased
generating conditions (42 W) and record the CPU core
from Sinopharm Chemical Reagent Co., Ltd. Pure SiC nanorods were
temperature (TCPU core). As the results presented in Figure 6b, it obtained from Changsha Sinet Advanced Materials Co., Ltd. All
can be seen that the TCPU core of the case using GHP as TIM chemicals were of analytical reagent grade and used without further
increases more slowly than that of 5000S35 and always shows a purification.
lower value (e.g.: ΔT = 6.3 °C at 780 s). And the comparative Preparation of SiO2 Nanoparticle-Decorated GO. A hydrolysis
temperature profiles of the computer motherboard in Figure 6c method was employed to prepare SiO2 NPs-decorated GO. GO was
dispersed in a mixture of ethanol (240 mL) and deionized water (24
also indicate a lower temperature when GHP was used as TIM.
mL) with ultrasonication for 120 min. Then, 4 mL of ammonia was
As a result, our GHP is a very promising candidate to replace the added to this dispersion for adjusting the pH value, following by the
state-of-the-art thermal pad for real electronic cooling addition of 0.5 mL of TEOS. After hydrolysis with bath ultrasonication
applications. for 180 min, the product was collected by vacuum filtration and washed

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with deionized water several times until a neutral pH was reached. SiO2 Author Contributions
NPs-decorated GO was finally obtained by drying the product at 60 °C. ¶
W.D. and L.L. contributed equally in this work for conceiving
Fabrication of Graphene Hybrid Paper. Graphene sheets (450 and designing the preliminary experiments. W.D. and C.T.L.
mg) and as prepared SiO2 NPs-decorated GO (50 mg) were uniformly wrote the paper and revised the manuscript at all stages. H.H.,
dispersed in ethanol via ultrasonic treatment. The dispersion was then
filtered through a Teflon filter membrane (pore size: 0.22 μm) to obtain
Q.Y., and X.T. performed partial materials characterization
a thin paper. The paper with the intercalation of SiO2 NPs was treated including Raman, XRD and XPS. J.L., Y.L., S.D., and X.X.
in high-frequency furnace at 1400 °C for 4 min. A graphene paper as a provided the NEMD and heat flux simulation and data analysis.
control sample was also made of 500 mg graphene sheets without SiO2 N.J. measured the EELS sprectra of the sample and contributed
NPs decoration using the same experimental process. reagents, materials, and analysis tools. X.Z., J.Y., Q.W., and J.W.
Characterizations. Raman spectra were recorded using a Reflex helped the mechanism explanation and assisted with the
Raman System (Renishaw PLC) employing a laser wavelength of 532 revision. R.S., J.X., N.J., and C.P.W. provided some constructive
nm. TEM images were taken by JEM-2100 (JEOL) with an acceleration suggestions and supervised this study.
voltage of 200 kV. Electron energy loss spectroscopy was performed
with a Gatan parallel spectrometer, and the corresponding analysis was Notes
conducted using the scanning transmission electron microscopy The authors declare no competing financial interest.
(STEM) mode of TEM. The surface morphology of the samples was
examined with field emission scanning electron microscopy (Quanta ACKNOWLEDGMENTS
FEG250, FEI). X-ray diffraction patterns were recorded by D8 Discover The authors are grateful for the financial support by the National
with GADDS (Bruker) with CuKa radiation (λ = 1.54 Å). X-ray Key R&D Program of China (grant no. 2017YFB0406000),
photoelectron spectroscopy was carried out with an AXIS Ultra DLD Scientific Instrument Developing Project of the Chinese
spectrometer (Kratos Analytical). The compression tests were carried
out on an electron omnipotence tester of universal testing machine Academy of Sciences (grant no. YZ201640), the Project of the
(UTM, 5567A, Instron). All samples were fabricated into a standard Chinese Academy of Sciences (grant no. KFZD-SW-409),
size. The loading rate was controlled as 0.1 mm min−1. Thermal Science and Technology Major Project of Ningbo (grant nos.
conductivity of the samples was measured with an LFA 467 NanoFlash 2016S1002 and 2016B10038), and the International S&T
apparatus (Netzsch). The IR photos were captured by using an infrared Cooperation Program of Ningbo (grant no. 2017D10016) for
camera (Fluke, Ti400). financial support. We also thank the Chinese Academy of
Sciences for Hundred Talents Program, Chinese Central
ASSOCIATED CONTENT Government for Thousand Young Talents Program, 3315
Program of Ningbo, and the Key Technology of Nuclear Energy
*
S Supporting Information
(CAS Interdisciplinary Innovation Team, 2014).
The Supporting Information is available free of charge on the
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