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 Mater. Res. Express 5 (2018) 065606 https://doi.org/10.1088/2053-1591/aacb59

PAPER

Direct synthesis of vertical graphene nanowalls on glass substrate for

thermal management
RECEIVED
14 April 2018
REVISED
30 May 2018
ACCEPTED FOR PUBLICATION
Nan Zhang1, Jiurong Li1, Zhiduo Liu2, Siwei Yang3, Anli Xu1, Da Chen1,6 , Qinglei Guo4,5,6 and
8 June 2018 Gang Wang1,6
1
PUBLISHED Department of Microelectronic Science and Engineering, Faculty of Science, Ningbo University, Ningbo 315211, People’s Republic of
27 June 2018 China
2
State Key Laboratory of Integrated Optoelectronics, Institute of Semiconductors, Chinese Academy of Sciences, Beijing 100083, People’s
Republic of China
3
State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Shanghai,
200500, People’s Republic of China
4
Department of Materials Science, Fudan University, Shanghai 200433, People’s Republic of China
5
Department of Materials Science and Engineering, Frederick Seitz Materials Research Laboratory, University of Illinois at Urbana-
Champaign, Urbana, IL 61801, United States of America
6
Authors to whom any correspondence should be addressed.
E-mail: chenda@nbu.edu.cn, guoqinglei@fudan.edu.cn and gangwang@nbu.edu.cn

Keywords: plasma-assisted chemical vapor deposition, graphene nanowalls, thermal management

Abstract
Vertical few layered graphene (VG) nanoflakes were directly synthesized on traditional glass substrate
by the plasma-assisted chemical vapor deposition, where the extremely low growing temperature
(<560 °C) and short time (<30 min) were involved. The VG microstructure could be well-controlled
by tuning the plasma power, growth time and growth temperature. Raman, TEM, and SEM were used
to determine the quality and single size of the VG. Because of the unique three-dimensional structure
with high surface area, the VG network can provide superior thermal management capabilities, which
has been demonstrated by the scalable frost removal. We believed that this hybrid system consisting of
vertical graphene nanowalls and glass substrates has great potentials for future transparent ‘green-
warmth’ constructions.

Graphene is a specific two-dimensional material with single carbon atoms patterned in hexagonal honeycomb
lattice structure. As the unique combination of high specific surface area, mechanical strength, chemical
stability, flexibility, high electrical and thermal conductivity, graphene is considered as a promising candidate in
photocatalysis, transparent electrodes, supercapacitors, and photodetectors [1–3]. For synthetic methodologies
of graphene, chemical vapor deposition is the superior and controllable method to grow large-size and few-
layered graphene, where centimeter-scale graphene single crystals have been realized on solid metal substrate
[4]. However, traditional CVD method requires a relatively high growth temperature (∼1000 °C), catalyst
substrates (e.g., Cu or Ni), and post-transfer or additional catalyst removal processes. During the transfer
procedure, loss of substrate material and the introduction of defects and contaminations, such as wrinkles,
holes, and metal etching residues on the films, would potentially impede the further applications [5]. In order to
bypass the transfer process, intense efforts have been pursued to develop transfer-free routes for the direct
synthesis of graphene on various dielectric substrates such as SiO2 [6], Si3N4 [7], Al2O3, and h-BN [8, 9]. Among
the proposed approaches, plasma-assisted chemical vapor deposition (PACVD), utilizing reactive spices
generated in the plasma, has exhibited significant advantages in lowering the growth temperature of
conventional 2D graphene, as well as vertical graphene (VG) nanowalls [10].
In our daily life, glass is a commonly used transparent and insulating amorphous oxide, with high surface
hydrophilicity and low thermal conductivity. Combining graphene with glass can significantly improve the
electrical and thermal properties of the glass while its transparent nature can be maintained. Various
applications such as energy-saving smart windows [11], heating devices [7], cell culture [12], cost-effective

© 2018 IOP Publishing Ltd

Mater. Res. Express 5 (2018) 065606 N Zhang et al

Figure 1. (a) Schematics of the lab-built PACVD system and VG nanowalls on glass. (b) Raman results of VG nanowalls deposited at
the constant temperature (550 °C) and plasma power (400 W), and at varying growth times. (c) Photographs and contact angles of
water droplets on VG nanowall/glass with different growth times. The insert shows the demonstration of the hydrophobic and
hydrophilic nature of graphene/glass (the right part) and the bare glass (the right part), respectively. (d) Optical transmittance spectra
in the wavelength range of 350–1000 nm of the graphene walls grown for 2, 10, 20, and 30 min. The insert shows the photographs of
the samples.

electrodes [13], and touch panel [14], have been realized on graphene/glass hybrids. In this work, we realized a
novel hybrid system that consists of VG nanowalls and glass substrates, which was further exploited for the
application in thermal management. The hybrid system was simply obtained by the PACVD without any
catalyst, where the growing temperature and time can be also decreased smaller than 560 °C and 30 min,
respectively. Qualities, properties and micro-morphologies of VG nanowalls are strongly depended on the
plasma power, growth temperature and growth time. Our work may provide very promising potentials for
scalable transparent ‘green-warmth’ constructions.
Glass substrates were chemically cleaned to remove all types of contaminants. Then glass pieces were put
into the horizontal quartz tube and fixed on an Al2O3 platform. Prior to heating, the quartz tube was evacuated
to approximately 10−5 mbar. Then continuous flows of 10 sccm argon (Ar) and 1 sccm hydrogen (H2) were
introduced until the tube pressure reaching 0.14 mbar. After heating to the desired temperature, 5 sccm
methane (CH4) was introduced to deposit VG nanowalls for different time durations (from 2 min to 30 min)
with varied plasma powers (IRF, changed from 100 W to 400 W). After switching off the plasma power and CH4
gas flow, the furnace was naturally cooled to room temperature. The synthesized VG nanowalls were
characterized using Raman spectroscopy (SENTERRA), transmission electron microscopy (TEM, FET-Tecnai)
and scanning electron microscopy (SEM, Magellan 400).

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Mater. Res. Express 5 (2018) 065606 N Zhang et al

Figure 2. (a) SEM images of VG nanowalls directly grown on glass substrates with the varying plasma power of 100 W, 200 W, 300 W
and 400 W. (b) SEM images of VG nanowalls directly grown on glass substrates with the varying growth temperature of 475 °C,
500 °C, 525 °C, and 550 °C. (c) Raman results of the obtained VG nanowalls deposited at the varying plasma power of 100 W, 200 W,
300 W and 400 W. (d) Raman results of the obtained VG nanowalls deposited at the varying growth temperature of 475 °C, 500 °C,
525 °C, and 550 °C.

The schematic diagram of the PACVD system, utilized for growing VG nanowalls on glass substrates, is
shown in figure 1(a). VG nanowalls obtained at various growth times were measured by Raman spectroscopy
with a 532 nm excitation laser. As shown in figure 1(b), all samples have three primary Raman peaks, locating at
about 1350 cm−1, 1580 cm−1 and 2680 cm−1, which are referred as the D band, G band, and 2D band. The high
D band existing in all samples can be attributed not only to the defects inside the graphene domains, but also to
the high fraction of open edges of small-sized VG nanowalls [15]. Furthermore, all samples have shoulder peaks
at about 1620 cm−1, which are assigned as D‘-peaks. Generally, the D′-peak is associated with defects and edges
of graphene. Therefore, the synthesized VG nanowalls exhibit a relatively low order of graphitization with a large
amount of inter-crystalline defects. The grain size of VG nanowalls can be estimated by the intensity ratio of
ID/IG, according to the equation ID/IG=C(λ)/La, where La is the grain size, λ is the wavelength of incident light
and C(λ) is a constant calculated as C(λ)=2.4×10−10×λ4 [16]. From the above equation, the grain sizes of
VG nanowalls are found to gradually increase from 9.6 to 18.0 nm with the increase of the growth time (from
2 min to 30 min), indicating that the size of VG nanowalls gradually grows. Because the 3D microstructure of the
erected graphene nanowalls can dramatically alter the wettability of the substrate [17, 18], characterizations of
contact angle of VG nanowalls under different growing times can, therefore, provide reliable evaluations on the
VG nanowall size growing process. As shown in figure 1(c), the contact angle of VG nanowalls with a growth
time of 2 min is 63°. And the contact angle increases with the extension of growth time, which reaches to 129° as
the growth time increases to 30 min, indicating that the size and density of the VG nanowalls play vital roles in
modifying the wettability of the surface. Optical images in the inset of figure 1(c) display a 2 cm×1.5 cm bare
glass (left) and a same size graphene/glass sample (right) after performing water dropping tests. For the bare
glass, film-wise water aggregations were formed, however, small water droplets can stand up on the VG
nanowalls coated glass. This phenomenon indicates that the graphene nanowalls surface have a hydrophobic
nature similar to the result of transferred graphene-on-glass system [18]. On the other hand, the VG nanowalls

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Mater. Res. Express 5 (2018) 065606 N Zhang et al

Figure 3. Characterizations of homogeneous VG nanowalls. (a) Raman spectrum of VG nanowalls on glass substrate. FWHM and
Lorentzian fitting of the 2D band are shown in the insert. (b) SEM image of VG nanowalls. (c) Cross-section SEM image of VG
nanowalls. (d) TEM image of VG nanowalls. The insert is the SAED pattern.

directly grown on glass substrates by PACVD possess outstanding optical properties. Photographs of as-
prepared samples grown for 2, 10, 20, and 30 min are shown in the insert of figure 1(d). The alphabets ‘NBU’ on
printing-papers, cover with VG nanowalls/glass under varying growing times, can be still seen, which intuitively
verifies the excellent transparency. It should be noticed that after nanowalls growth, the transparency of the VG
nanowalls/glass decreases with increasing growth time (from left to right), representing significant capabilities
of tuning the optical properties of as-fabricated samples by adjusting the growth time. Herein, the transparency
is reflected by the UV–vis transmittance spectra. For instance, the transparency at 550 nm is 90.4% for the 2 min
growth sample, and reaches 86.9%, 83.1% and 79.3% when the growing time extends to 10 min, 20 min and
30 min, respectively.
In addition to the growth time, plasma power and growth temperature also affect the quality and
morphology of VG nanowalls. In order to obtain high quality VG nanowalls, optimized growth conditions are
investigated. Firstly, the growth condition of plasma power was optimized. Figures 2(a1)–(a4) shows the SEM
images of the samples with different plasma powers (from 100 W to 400 W). It is found that with the increase of
plasma power, the VG nanowalls gradually grow, reaching the largest nanowall size and condensed density when
the power was set to be 400 W. On the other hand, the growth temperature also exhibits vital roles in modifying
the morphology of VG nanowalls, as shown in figures 2(b1)–(b4). As the growth temperature increases from
475 °C to 550 °C, the size and condensed density of VG nanowalls increase as well. Raman spectra of the as-
prepared VG nanowalls on glass substrates with different plasma powers and growth temperatures are shown in
figures 2(c)–(d). The growth time was constant to be 30 min. As the plasma power (from 100 W to 400 W) and
the growth temperature (from 475 °C to 550 °C) increase, all ID/IG extracted from the Raman results exhibits
the similar varying tendency with a gradual decrease, further demonstrating the gradual growing of VG
nanowalls sizes. Meanwhile, the I2D/IG gradually increases, indicating that the quality of the nanowalls gets
better. From what has been discussed above, the optimized growth conditions for obtaining VG nanowalls with
large grain size and high quality were 550 °C, 400 W, and 30 min.

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Mater. Res. Express 5 (2018) 065606 N Zhang et al

Figure 4. (a)–(d) Digital images of the defogging process at a bias of 5 V. (e) Cycling performance of the defogging at different input
biases.

Based on the above optimized growth conditions (i.e., temperature: 550 °C; duration time: 30 min; plasma
power: 400 W), polycrystalline VG nanowalls were directly deposited on glass substrates by PACVD. Figure 3(a)
shows the representative Raman spectrum of the deposited VG nanowalls, and a bare glass slide was also
measured for comparison. Three primary peaks, D peak at ∼1350 cm−1, G peak at ∼1580 cm−1, and 2D peak at
∼2680 cm−1 can be found. The insert shows the symmetric 2D peak with a full-width at half-maximum
(FWHM) of ∼50 cm−1, indicating a multilayer feature of the obtained VG nanowalls [19]. Figure 3(b) shows a
typical SEM image of VG nanowalls, in which continuous flower-like three-dimensional network structure can
be found. The average size of the VG nanowalls is around 300–350 nm. It has a sheet resistance of less than
250 Ω/cm2. The cross-section image suggests that these VG nanowalls are around 330 nm in height, as shown in
figure 3(c). The suspended VG nanowalls on the TEM grids are continuous with wrinkle and overlap, as shown
in figure 3(d), and the SAED pattern in the insert shows an ambiguous diffraction ring pattern, which confirms
that the graphene is a typical polycrystalline structure. To demonstrate the feasibility of the optimized VG
nanowalls that are applied for thermal management, a transparent heater was demonstrated and exploited as the
defroster device. The optical transmittance of the transparent heater, with a large active working area of
2×2 cm2, can reach ∼80% (not shown here). As demonstrated in figures 4(a)–(d), the device offers an
advanced defrosting performance with a defrost completion time of 8 s when the applied bias was 5 V. Due to the
superior conductibility and hydrophobicity of graphene, the surface temperature of VG nanowalls
monotonically increases over time when applied with an electrical power, leading to an effective defrosting.
Figure 4(e) shows the cycling performance of the defogging display made under different input voltages of 5 V–
40 V, and no noticeable deterioration can be observed even after repetitive tests of twenty-five cycles, implying a
stable defogging behavior. The proposed device shows comparable performance with that of metal-wire-based
defrosting windows in modern vehicles or antifogging mirror in bathroom, while provides superior advantages
compared to that of bare glass substrates under identical conditions. The defrosting performances demonstrate
that hybrid systems of VG nanowalls and glass substrates have great potential for future transparent ‘green-
warmth’ constructions, as well as novel thermal management devices.
In summary, we describe a facile method for directly synthesizing polycrystalline VG nanowalls on glass
substrates by PACVD. The quality of VG nanowalls can be simply controlled via tuning growth conditions. To
demonstrate the thermal management potential of the as-grown VG nanowalls, a larger-area transparent defroster
device was constructed. Our work may pave the way for the scalable production of high-quality VG nanowalls, and
offers enormous opportunities for the next generation of industrial-level thermal management devices.

Acknowledgments

We acknowledge the financial support from National Natural Science Foundation of China under Grant (Nos.
61604084, 11704204 and 51602056), Foundation of Zhejiang Educational Commission (No. Y201635454),

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Mater. Res. Express 5 (2018) 065606 N Zhang et al

General Financial Grant from China Postdoctoral Science Foundation (No. 2015M581523), K C Wong Magna
Fund in Ningbo University and the Natural Science Foundation of Ningbo under Grant (No. 2017A610104). Q
L Guo acknowledges the support under the International Postdoctoral Exchange Fellowship Program by the
Office of China Postdoctoral Council.

ORCID iDs

Da Chen https://orcid.org/0000-0002-0334-9502

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