Carbon 126 (2018) 472e479

Contents lists available at ScienceDirect

Carbon
journal homepage: www.elsevier.com/locate/carbon

Laser-induced graphene fibers

Luong Xuan Duy a, b, Zhiwei Peng b, Yilun Li b, Jibo Zhang b, Yongsung Ji b,
James M. Tour b, c, d, *
a
Applied Physics Program, Rice University, 6100 Main Street, Houston, TX, 77005, USA
b
Department of Chemistry, Rice University, 6100 Main Street MS 222, Houston, TX, 77005, USA
c
Department of Material Science and NanoEngineering, Rice University, 6100 Main Street, Houston, TX, 77005, USA
d
Smalley-Curl Institute and the NanoCarbon Center, Rice University, 6100 Main Street, Houston, TX, 77005, USA

a r t i c l e i n f o a b s t r a c t

Article history: In our previous research, we found that the laser induction process on commercially available polyimide
Received 19 August 2017 sheets is a cost-effective method for the formation of porous graphene that can be subsequently fabri-
Received in revised form cated into mechanically flexible devices. Here we study the parameters required for the formation of
9 October 2017
varied laser-induced graphene (LIG) morphologies by tuning the laser radiation energy. It was found that
Accepted 11 October 2017
a critical fluence point of ~5 J/cm2 is needed to initiate the carbonization process regardless of the laser
Available online 13 October 2017
power. When increasing the radiation energy, the physical formation of LIG follows a fluid dynamics
process in that the morphology of the LIG progressively changes from sheets to fibers and finally to
Keywords:
Laser induced graphene
droplets. We then demonstrate that a morphology of LIG nanomaterial, LIG fibers (LIGF), can be
Laser induced graphene fibers generated by this one-step laser photothermolysis process at a radiation energy >40 J/cm2. The LIGF are
Laser photothermolysis hollow with a LIG wall and form vertically aligned fibers up to 1 mm in height. Microsupercapacitor
Polymer carbonization (MSC) devices fabricated from LIGF and LIGF-LIG hybrids show 2
the specific areal capacitance over
Microsupercapacitor MSCs made entirely from LIG, thereby underscoring the potential for LIGF in flexible device applications.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction [25]. Additionally, synthesis of these carbon nanomaterials from

The discovery of carbon based nanomaterials such as the ful-
lerenes [1], carbon nanotubes (CNTs) [2], and graphene [3] has led
to large investments in carbon-based nanotechnology research.
Carbon nanomaterials have been extensively studied, revealing
their outstanding chemical, physical, electrical, mechanical, optical,
and thermal properties, many of which are not possible to achieve
using other materials [4e8]. Because of their extraordinary per-
formances, these carbon nanomaterials have been widely used in
numerous applications such as in transistors [9e12], biological and
chemical sensors [13,14], energy generation/storage devices
[15e20], and polymer nanocomposites [21,22].
In order to fully realize their potential in different applications,
various derivatives and morphologies of these carbon nano-
materials have been developed such as graphene oxide (GO) [23],
vertically aligned CNTs [24], and graphene nanoribbons (GNRs)
* Corresponding author. Department of Chemistry, Rice University, 6100 Main
Street MS 222, Houston, TX, 77005, USA.
E-mail address: tour@rice.edu (J.M. Tour).
inexpensive precursors [26] using cost-effective processes [27] is
highly desired for industrial production. Recently, our group
developed a simple and effective method to make porous graphene
from commercial available polyimide (PI) sheets by laser induction
under ambient conditions [28]. In these studies, the resulting
product, laser-induced graphene (LIG), was found to contain few-
layer graphene with high electrical conductivity, high thermal
stability, high thermal conductivity [29] and outstanding electro-
chemical performance. Wetting properties of LIG can be alternated
from superhydrophobic to superhydrophilic by conducting the
laser process under different controlled atmospheres [30]. A major
application of LIG is for microsupercapacitors (MSCs) that have an
in-plane interdigitated shape or sandwiched structure [31]. The
capacitance of the first generation of LIG-MSCs was 4 mF/cm2,
comparable to other carbon based MSCs. Follow-up studies
increased the capacitance to 16 mF/cm2 by the use of a solid-state
electrolyte and boron doping [32]. Additional research introduced
pseudocapacitive materials into LIG devices by electrochemical
deposition, and the capacitance value further increased to 950 mF/
cm2 [33]. Another application of metal-salt-containing PI films
resulted in LIG that contained metal oxide nanoparticles suitable as

https://doi.org/10.1016/j.carbon.2017.10.036
0008-6223/© 2017 Elsevier Ltd. All rights reserved.
 L.X. Duy et al. / Carbon 126 (2018) 472e479
oxygen reduction reaction (ORR) catalysts [34].
Before the development of LIG, carbonization of PI was shown to
afford a porous structure by ultraviolet exposure [35,36] but gra-
phene was not disclosed and there have been no studies on the
precise parameters required to afford the various possible mor-
phologies. In this work, we detail parameters for the controlled
formation of varying LIG morphologies. When changing the total
radiation energy per unit area on PI, it was found that a critical
fluence point of ~5 J/cm2 is needed to initiate the carbonization
process. Furthermore, a form of LIG that we call LIG fibers (LIGF) is
disclosed here by lowering the consecutive laser pulse stacking
density. By applying a commercial CO2 laser raster mode, the ver-
tical growth of a forest of LIGF with a height of 1 mm was afforded
in one step. Analyses to confirm the graphene-based properties of
LIGF are presented. The effect of a 9.3 mm wavelength laser was
compared to the previously used 10.6 mm wavelength laser and
parameters have been developed to reliably control the LIG vs LIGF
morphologies for device optimization. Finally, interdigitated MSCs
from LIGF and LIGF-LIG hybrids are disclosed here.
2. Experimental
2.1. Synthesis of LIGF
Kapton PI (Cat. No. 2271K6, thickness: 0.00500 ) was purchased
Fig. 1. SEM images of samples with fluence set at (a) 4.4 J/cm2, (b) 4.9 J/cm2 and (c) 5.5 J/cm2; the insets in each SEM image are optical microscope images of the same spot. (d)
Raman spectra of the laser spot as fluence was increased (from top to bottom). Inset optical microscope scale bar: 50 mm. The laser induction was performed with a 10.6 mm 75 W
laser in vector mode. (A colour version of this figure can be viewed online.)
473
from McMaster-Carr and used as received. Laser induction was then
conducted on a PI sheet with a 10.6 mm and 9.3 mm CO2 laser cutting
system (Universal XLS10MWH platform). All experiments were
performed under ambient conditions. The single laser pulse were
done in vector mode and the LIGF forest synthesis was done in
raster mode (see Supporting Information).
2.2. Characterization
Scanning electron microscopy (SEM) images were obtained on a
JEOL 6500F SEM. Transmission electron microscopy (TEM) and high
resolution TEM (HRTEM) images were obtained using a JEOL 2100F
field emission gun transmission electron microscope. TEM samples
were prepared by scratching LIGF from the PI substrate, followed by
sonication in chloroform, and dropping the slurry onto a lacey
carbon copper grid. Raman spectra were recorded on a Renishaw
Raman microscope using a 514 nm laser with a power of 5 mW. X-
ray diffraction (XRD) was conducted on a Rigaku D/Max Ultima II
with Cu Ka radiation (l ¼ 1.54 Å). X-ray photoelectron spectroscopy
(XPS) was performed using a PHI Quantera SXM Scanning X-ray
Microprobe with a base pressure below 5
108 torr. Survey
spectra were recorded in 0.5 eV step size with pass energy of
140 eV. Elemental spectra were recorded in 0.1 eV step sizes with
pass energy of 26 eV. All of the spectra were corrected using the C1s
peak (284.5 eV) as reference. The surface area of LIGF was measured
474
with a Quantachrome autosorb-3b Brunauer-Emmett-Teller (BET)
surface analyzer.
2.3. Fabrication of the flexible all-solid-state MSCs
Poly(vinyl alcohol) (PVA)/H2SO4 was used as the solid electro-
lyte for all of the devices. It was made by stirring deionized (DI)
water (10 mL), sulfuric acid (1.0 mL, 98%, Sigma-Aldrich), and PVA
(1.0 g) at 80  C overnight. ~0.25 mL of the electrolyte was applied to
the active area of the devices, and was dried under ambient con-
ditions for 4 h. The all-solid-state MSCs were obtained after drying
in a vacuum desiccator (~120 mm Hg) overnight for further solid-
ification of the electrolyte.
3. Results and discussion
3.1. Fluence as unit of carbonization
A commercial Universal Laser System XLS10MWH laser cutter
platform is used as the laser source operated in pulse width mod-
ulation (PWM) and equipped with two 10.6 mm wavelength lasers
at 75 W and 10 W and one 50 W 9.3 mm wavelength laser. This type
of laser system is routinely employed in machine shops; hence it is
readily accessible. In our previous study [28], a porous LIG structure
with a few-layer graphene structure was generated during laser
induction under ambient conditions at room temperature when a
CO2 laser (10.6 mm) was focused on the surface of PI sheets with a
laser power of 60 W in 4%e10% duty cycles at a frequency of 6 kHz
and 1000 pulses per inch (PPI) (note that inches are used since that
is the commercial instrument setting basis). Under such conditions,
the thickness of the LIG on the surface of PI sheets was <50 mm
regardless of the duty cycle. Here, we first study the interaction of
individual laser pulses upon PI from the 10.6 mm 75 W laser. To
single out each pulse, the laser pattern is set in vector mode (in
which the laser moves in a line pattern) with pulse separation from
30 to 400 PPI. The laser radiation energy density, or fluence, was
measured by averaging many pulses (see laser parameters in the
Supporting Information and Figs. S1eS3).
Raman spectroscopy was used as a tool to determine when
carbonization began, with confirmation from optical microscopy. In
Fig. 1, Raman spectra at a low fluence of ~4.4 J/cm2 had an
appearance similar to that of bulk PI, indicating that little or no
carbonization occurred, which agrees with the lack of black carbon
Fig. 2. SEM images of PI samples as the laser fluence was increased. a,b) 3.5 J/cm2; c,d) 4.0 J/cm2; e-h) 5.8 J/cm2. The laser induction is performed with a 10.6 mm 75 W laser in vector
mode. (A colour version of this figure can be viewed online.)
L.X. Duy et al. / Carbon 126 (2018) 472e479
noted in the optical image (Fig. 1a). When the laser fluence was
increased to ~4.9 J/cm2, D and G peaks at ~1350 cm1 and
~1590 cm1 were visible in the Raman spectrum, suggesting that
carbonization had begun (Fig. 1b). The optical image confirmed
carbonization with the appearance of a black spot. Note that the
surface of the PI sheet is kept scratch-free during experiments
because surface roughness can cause a fluence reduction at the
carbonization point. When the laser fluence was further increased
to ~5.5 J/cm2, the appearance of the 2D peak at ~2700 cm1,
resulting from second order zone boundary phonons [37], suggests
more complete graphitization of PI and formation of graphene
(Fig. 1c). Laser irradiation (W/m2) and pulse duration are not used
as carbonization units because the laser pulse profile is not
continuous but an exponential rise followed by exponential decay.
Therefore, fluence is the better choice for determining the
carbonization unit. To confirm this conclusion, the 75 W laser was
defocused and the 10 W laser was used to vary the irradiation. With
irradiation ranging from 22 to 265 GW/m2, the same fluence of ~5 J/
cm2 is necessary for carbonization (Fig. S4). This fluence range is
well within the range for commercial CO2 laser systems where the
laser power is 10e100 W and the laser spot size is 50e100 mm. At
this range, the heat loss by thermal conduction is negligible.
SEM examination of the fine structure generated at different
fluence points interestingly reveals what might have been the dy-
namics of the carbonization process. PI is known for its oxygen and
nitrogen outgassing at 550  C, followed by carbonization at 700  C
and finally graphitization at 3000  C [38,39]. As a result of rapid
outgassing from the PI melt, it undergoes fluid fragmentation. Ev-
idence of PI liquefying during the laser-induced process is shown in
the stress test in Figs. S5 and S6. Previous studies showed the fluid
dynamics of such breakup results in a cascade of sheets, fibers and
droplets [40]. We observed similar dynamics in the laser induction
process that can be divided into the following four stages (Fig. 2,
more detail in Fig. S7): (1) At low fluence (3.5 J/cm2) as in Fig. 2a and
b, the carbonization is limited due to low energy input and a ma-
jority of the formed nanostructures are thin sheets of PI. (2) At
higher fluence (4.0 J/cm2), the sheet nanostructure starts to break
into fibers (Fig. 2c and d). One transition from sheets to fibers is
indicated with a blue arrow in Fig. 2d. (3) At a fluence point high
enough for carbonization (5.8 J/cm2), as shown in Fig. 2eeg, sheet
and fiber features remain but in graphitic form as indicated by
strong D and 2D peaks in the Raman spectra (Fig. 1d). (4) At this
high fluence point, the transition from fiber to carbonized droplets
 L.X. Duy et al. / Carbon 126 (2018) 472e479 475

Fig. 3. (a) Schematic of laser raster mode. (b) LIG and LIGF height dependence on laser fluence. (c) SEM images of LIG induced by 117 J/cm2 laser fluence made at 1000 PPI image
density setting (d) 500 PPI, 46 J/cm2 LIGF surface; (e) LIGF at higher magnification. (f) 166 J/cm2 LIGF with thickness of ~1 mm made at 500 PPI image density setting. (g) LIG at the
interface of LIGF and PI. (h) “R” shape patterned LIGF. Insets of c and f are schematics for 1000 PPI and 500 PPI, respectively. (A colour version of this figure can be viewed online.)
476 L.X. Duy et al. / Carbon 126 (2018) 472e479
can be observed as shown in Fig. 2g and h. These carbonized
droplets form carbon nanoparticles (CNPs) that are mostly blown
away by the laser air assist. In comparison, for samples at the same
fluences but with the 10 W 10.6 mm laser, similar fluence for
carbonization is observed, but the morphology slightly favors the
sheet-like structures (Fig. S8).
3.2. Vertically aligned LIGF forest
All commercial laser cutting systems have two modes, vector
and raster. In vector mode, the laser follows a pattern in both the x
and y direction. In the raster mode, the laser scans the 2D pattern in
the x-direction only (Fig. 3a). We changed the laser induction
process from vector mode to raster mode in order to prepare a large
area of LIG material. Fluence is measured as accumulated energy
over a unit area. Similar to other commercial laser systems, the
image density is controlled by the following two factors: the pulse
width modulation or PPI, and the lines per inch (LPI), both an
indication of the density of the laser lines. Our previous reports
were done at 1000 PPI
1000 LPI (pulse separation 25.4 mm) with a
laser spot size of ~100 mm, resulting in a LIG thickness of ~30 mm
[28]. In that case, the laser spots induced on the PI surface over-
lapped, leading to overheating and destruction of the top LIG layers,
thus resulting in the remaining LIG layers having thickness <50 mm
regardless of the fluence (Fig. 3b and c). In order to preserve the LIG
layers, which turn out to be LIGF, an image density of
500 PPI
500 LPI (pulse separation 50.8 mm) with a laser spot size
of ~60 mm was used to ensure that each pulse was well-separated
from its neighboring pulse (Fig. 3d). It was found that this image
density is the most crucial parameter that determines the final LIG
morphology; higher image density favors the sheet-like structure
LIG and lower image density favors the fiber-like structure LIGF. The
resulting height-controllable and tubular nanostructure LIGF has a
vertically aligned forest morphology. The laser system provides a
Fig. 4. (a) Raman spectra of the carbon layer resulting from variable fluence lases of 9.3 mm laser with optical image insets. (b) SEM image of a LIGF forest made with a 9.3 mm laser
and 25.2 J/cm2 fluence. (c) LIGF height of both 10.6 mm and 9.3 mm lases with variable fluences. (A colour version of this figure can be viewed online.)
lateral resolution of 2 mm that provides high resolution spacing
between each column and row. In Fig. 3eeg, using a laser pulse
with fluence of 166 J/cm2, a LIGF forest with ~1 mm height was
synthesized before the 120 mm-thick PI substrate was entirely
converted to LIGF. It must be noted that the laser treatment process
is relatively fast: 1 min for a 1 cm2 pattern even at low raster speed.
A thin LIG layer of ~30 mm was also found at the interfaces between
the LIGF and PI (Fig. 3g). A conductivity test showed seamless
electrical conductance between the interfacial LIG and LIGF forest
(Fig. S9 and Table S1). The LIGF forest can be patterned with a
resolution of the laser spot size (~60 mm). The optical system can be
improved for higher resolution but the limitation of the pattern
resolution is the diffraction limit (~5 mm, half of the 10.6 mm
wavelength). An “R” shape patterned LIGF was made to demon-
strate the laser system resolution capability (Fig. 3h).
In our previous report [28], we suggested that the carbonization
process is induced by a photothermal process. Therefore, higher
laser absorption would result in better carbonization. By Fourier
transform infrared spectroscopy (FTIR), the absorption of PI at
9.3 mm is ~2.3
larger than at 10.6 mm (Fig. S10a). In Fig. 4a, the
9.3 mm laser was used for the laser induction on PI sheets, and the
Raman and optical microscopy results reveal that the critical
carbonization point is ~2.1 J/cm2, ~2.3
less than the value 4.9 J/
cm2 when using the 10.6 mm laser. Even though the absorption and
critical point of carbonization agree well with each other, we
cannot completely attribute the fluence at carbonization only to the
absorption; other factors such as heat conductivity or changes of IR
absorption at higher temperatures might play a role. Nonetheless,
the agreement is interesting. The morphology differences can be
seen in Fig. S10b and c such that at high fluence, LIGF and CNPs are
favored nanostructures because with higher absorption at 9.3 mm,
only thin layers of PI receive the laser energy, possible resulting in
more abrupt liquid dynamics than obtained with the 10.6 mm laser.
Furthermore, as the fluence increases, the thickness of the LIGF
 L.X. Duy et al. / Carbon 126 (2018) 472e479
decreases, possibly because of the higher production of CNPs or
vaporization of the PI. If only hundreds of microns of LIGF are
needed, use of a strong absorption laser would be possible.
Otherwise, if the application needs LIGF at thicknesses of ~1 mm,
weak absorption lasers such as the 10.6 mm CO2 laser afford these
thick LIGF forests.
3.3. Characterization
To confirm the graphitic nature and elemental composition of
the obtained LIGF, Raman spectra, XRD and XPS spectra of LIGF
were obtained for a sample made with a fluence of 122 J/cm2. In
Fig. 5a, Raman spectra show a strong D peak at ~1350 cm1 induced
by defects or symmetry broken sites [41]. A sharp 2D peak at
~2700 cm1 with ~1.25 IG/I2D ratio indicates a few-layer graphene
structure [42] In the XRD, a prominent peak is observed at ~ 26 ,
representing the (002) graphitic crystal planes. This gives an
interlayer spacing of ~3.4 Å, well matched with the graphitic phase.
A (100) graphitic crystal phase is also shown at an angle of ~43 . By
XPS the content of oxygen in LIGF is 3% without XPS-detectible
nitrogen content. This is lower than the LIG made with a fluence
of 29 J/cm2, which has 1.1% nitrogen and 4.2% oxygen. The BET
surface area for the LIGF sample at ~160 J/cm2 fluence is 70 m2/g
(Fig. S11), less than that of LIG at 342 m2/g [28].
To investigate further the structure of LIGF, a LIGF/CHCl3 sus-
pension was dropped onto a lacey carbon grid for TEM character-
ization. Fig. 6 represents typical TEM images of the LIGF. In Fig. 6a,
LIGF are entangled together, but the alignment is roughly preserved
even after solution bath sonication. From HRTEM images in Fig. 6b
Fig. 5. (a) Raman spectrum of LIGF showing the D, G and 2D peaks. (b) XRD prominent peak is shown at ~26 , representing (002) graphitic crystal planes. (c) XPS survey spectra of
PI, LIG and LIGF. (d) XPS of C 1s content of PI, LIG and LIGF; (e) XPS of N 1s content of PI, LIG and LIGF; (f) XPS of O 1s content of PI, LIG and LIGF. (A colour version of this figure can be
viewed online.)
477
and c, LIGF showed a few-layer graphene structure with disordered
fringes found on the focal plane and ordered fringes near the edge
of LIGF. The highly disordered structure observed in the HRTEM
agrees well with the high ID/IG ratio seen in the Raman spectra. The
concentration of ordered fringes at the edges suggest graphitic
curves at the edges of the LIGF, resulting from the curving of LIG to
form LIGF. The synthesis of CNTs requires a growth seed [43,44].
The LIGF, instead of growing from a seed, are produced from LIG.
The evidence can be seen in Fig. 2b, d and e as the sheet structure
breaks down to smaller strips and eventually to a fiber. The point
that LIG tears and turns into LIGF is indicated by the blue arrow in
Fig. 6a. This can also be seen in the SEM images (Fig. 2d) where LIG
turns into LIGF. The hollow structure of LIGF can be seen in Fig. 5d
that shows the opening tip of an individual LIGF. Based on the BET
data, the fiber structure of LIGF has a lower surface area than does
LIG.
3.4. Results in MSC application
To highlight an application of LIGF, we fabricated an in-plane
interdigitated solid state MSC from LIGF and compared it to the
MSCs fabricated from LIG alone. The interdigitated device size with
neighboring electrode distances of 300 mm was kept the same as in
the previous report [28]. In Fig. 7, the fabricated LIGF-MSC has a
specific area capacitance higher than LIG-MSC by 50%. One of the
key elements of the MSC is the low sheet resistance. In Fig. S12, the
LIGF sheet resistance is 100e200 U/sq, 5
that reported for LIG at
20 U/sq. LIG that is fabricated with 1000 PPI (Fig. 3c inset) has more
overlapping of laser pulses than the LIGF that is fabricated with
478 L.X. Duy et al. / Carbon 126 (2018) 472e479

Fig. 6. HRTEM images of LIGF. (a) 50e100 nm diameter LIGF emanating from LIG. The blue arrow shows the point at which LIG coils into LIGF. (b) Typical LIGF ordered fringes. (c)
LIGF with size of 40e50 nm are also observed with ordered fringes in the edge with a distance of 3.4 Å. (d) The tip of single LIGF with an open end. (A colour version of this figure
can be viewed online.)

Fig. 7. (a) Specific area capacitance comparison of MSC made with LIG, LIGF and LIG-LIGF. (b) SEM image of the edge of the LIG-LIGF-MSC showed the incorporated ~50 mm of LIGF.
(A colour version of this figure can be viewed online.)

500 PPI (Fig. 3f inset). Thus, LIG is made with more electrically
conductive pathways, resulting in lower sheet resistance when
compared to LIGF. Therefore, to incorporate LIGF into LIG-MSC we
supplemented the LIG-MSC with a line of 50 mm LIGF. The specific
area capacitance increased ~2
when compared to that from LIG.
Most of the charge storage capacity is close to the edge of the
interdigitated LIG. Therefore, this LIG-LIGF hybrid increases the
amount of active materials where most of the charge is stored.
Hence, a small amount of LIGF introduced a large amount of charge
storage capacity into the MSC.
4. Conclusion
By tuning the laser parameters (operational modes, PPI, duty
cycle) we have produced LIGF, a different morphology than the LIG
foams made previously. The fluid dynamics process of the carbon-
forming event could be captured in the solidified material. A better
understanding of laser parameters gives us some control over the
 L.X. Duy et al. / Carbon 126 (2018) 472e479
carbon morphology, thus enabling the fabrication of millimeter-
scale vertically aligned LIGF forests. Further studies showed the
details of the graphitic hollow structure of LIGF. The application of
LIGF in MSCs results in 2
capacitance of LIG-LIGF-MSC over LIG-
MSC, indicating the potential of LIGF in flexible electronic device
configurations.
Conflict of interest
Rice University owns several patent filings on the laser induc-
tion process described here. That portfolio has been licensed to a
company in which none of the authors are officers, directors or
shareholders. J.M.T serves as a consultant to that company. Conflicts
of interest are managed through regular disclosure to and approval
from the Rice University Office of Sponsored Programs and
Research Compliance.
Acknowledgements
This work was funded by the AFOSR (FA9550-14-1-0111). D. X. L.
thanks the Vietnam Education Foundation for support. Rice Uni-
versity gratefully acknowledges generous support from Universal
Laser Systems for providing the XLS10MWH laser system with
Multiwave Hybrid™ technology that was used for this research,
and J. Hillman of Universal Laser System for helpful advice.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.carbon.2017.10.036.
References
[1] H.W. Kroto, J.R. Heath, S.C. O'Brien, R.F. Curl, R.E. Smalley, C60: Buckmin-
sterfullerene, Nature 318 (1985) 162e163.
[2] S. Iijima, Helical microtubules of graphitic carbon, Nature 354 (1991) 56e58.
[3] A.K. Novoselov, S.V. Geim, D. Morozov, Y. Jiang, S.V. Zhang, I.V. Dubonos,
A.A.F. Grigorieva, Electric field effect in atomically thin carbon films, Science
(80-) 666 (2013) 666e669.
[4] M.F.L. De Volder, S.H. Tawfick, R.H. Baughman, A.J. Hart, Carbon nanotubes:
present and future commercial applications, Science (80-) 339 (2013)
535e539.
[5] Y. Zhang, L. Zhang, C. Zhou, Review of chemical vapor deposition of graphene
and related applications, Acc. Chem. Res. 46 (2013) 2329e2339.
[6] D. Jariwala, V.K. Sangwan, L.J. Lauhon, T.J. Marks, M.C. Hersam, Carbon
nanomaterials for electronics, optoelectronics, photovoltaics, and sensing,
Chem. Soc. Rev. 42 (2013) 2824e2860.
[7] R.H. Baughman, A.A. Zakhidov, W.A. de Heer, Carbon nanotubesethe route
toward applications, Science (80-) 297 (2002) 787e792.
[8] M.J. Allen, V.C. Tung, R.B. Kaner, Honeycomb carbon: a review of graphene,
Chem. Rev. 110 (2009) 132e145.
[9] Q. Cao, S. Han, G.S. Tulevski, Y. Zhu, D.D. Lu, W. Haensch, Arrays of single-
walled carbon nanotubes with full surface coverage for high-performance
electronics, Nat. Nano 8 (2013) 180e186.
[10] C.-H. Liu, Y.-C. Chang, T.B. Norris, Z. Zhong, Graphene photodetectors with
ultra-broadband and high responsivity at room temperature, Nat. Nano 9
(2014) 273e278.
[11] F. Schwierz, Graphene transistors, Nat. Nanotechnol. 5 (2010) 487e496.
[12] S. Heinze, J. Tersoff, R. Martel, V. Derycke, J. Appenzeller, P. Avouris, Carbon
nanotubes as schottky barrier transistors, Phys. Rev. Lett. 89 (2002) 106801.
[13] Y. Shao, J. Wang, H. Wu, J. Liu, I.A. Aksay, Y. Lin, Graphene based electro-
chemical sensors and biosensors: a review, Electroanalysis 22 (2010)
1027e1036.
[14] D. Rodrigo, O. Limaj, D. Janner, D. Etezadi, F.J. García de Abajo, V. Pruneri,
H. Altug, Mid-infrared plasmonic biosensing with graphene, Science (80-) 349
(2015) 165e168.
[15] J. Ren, L. Li, C. Chen, X. Chen, Z. Cai, L. Qiu, Y. Wang, X. Zhu, H. Peng, Twisting
carbon nanotube fibers for both wire-shaped micro-supercapacitor and mi-
cro-battery, Adv. Mater 25 (2013) 1155e1159.
[16] S.N. Habisreutinger, T. Leijtens, G.E. Eperon, S.D. Stranks, R.J. Nicholas,
H.J. Snaith, Carbon nanotube/polymer composites as a highly stable hole
479
collection layer in perovskite solar cells, Nano Lett. 14 (2014) 5561e5568.
[17] F. Bonaccorso, L. Colombo, G. Yu, M. Stoller, V. Tozzini, A.C. Ferrari, R.S. Ruoff,
V. Pellegrini, Graphene, related two-dimensional crystals, and hybrid systems
for energy conversion and storage, Science (80-) (2015) 347.
[18] M.F. El-Kady, R.B. Kaner, Scalable fabrication of high-power graphene micro-
supercapacitors for flexible and on-chip energy storage, Nat. Commun. 4
(2013) 1475.
[19] E. Yoo, J. Kim, E. Hosono, H. Zhou, T. Kudo, I. Honma, Large reversible Li
storage of graphene nanosheet families for use in rechargeable lithium ion
batteries, Nano Lett. 8 (2008) 2277e2282.
[20] M. Kaempgen, C.K. Chan, J. Ma, Y. Cui, G. Gruner, Printable thin film super-
capacitors using single-walled carbon nanotubes, Nano Lett. 9 (2009)
1872e1876.
[21] G. Mittal, V. Dhand, K.Y. Rhee, S.-J. Park, W.R. Lee, A review on carbon
nanotubes and graphene as fillers in reinforced polymer nanocomposites,
J. Ind. Eng. Chem. 21 (2015) 11e25.
[22] K. Hu, D.D. Kulkarni, I. Choi, V.V. Tsukruk, Graphene-polymer nanocomposites
for structural and functional applications, Prog. Polym. Sci. 39 (2014)
1934e1972.
[23] D.C. Marcano, D.V. Kosynkin, J.M. Berlin, A. Sinitskii, Z. Sun, A. Slesarev,
L.B. Alemany, W. Lu, J.M. Tour, Improved synthesis of graphene oxide, ACS
Nano 4 (2010) 4806e4814.
[24] K. Hata, D.N. Futaba, K. Mizuno, T. Namai, M. Yumura, S. Iijima, Water-assisted
highly efficient synthesis of impurity-free single-walled carbon nanotubes,
Science (80-) 306 (2004) 1362e1364.
[25] D.V. Kosynkin, A.L. Higginbotham, A. Sinitskii, J.R. Lomeda, A. Dimiev,
B.K. Price, J.M. Tour, Longitudinal unzipping of carbon nanotubes to form
graphene nanoribbons, Nature 458 (2009) 872e876.
[26] Z. Yan, J. Lin, Z. Peng, Z. Sun, Y. Zhu, L. Li, C. Xiang, E.L. Samuel, C. Kittrell,
J.M. Tour, Toward the synthesis of wafer-scale single-crystal graphene on
copper foils, ACS Nano 6 (2012) 9110e9117.
[27] Z. Yan, Z. Peng, Z. Sun, J. Yao, Y. Zhu, Z. Liu, P.M. Ajayan, J.M. Tour, Growth of
bilayer graphene on insulating substrates, ACS Nano 5 (2011) 8187e8192.
[28] J. Lin, Z. Peng, Y. Liu, F. Ruiz-Zepeda, R. Ye, E.L.G. Samuel, M.J. Yacaman,
B.I. Yakobson, J.M. Tour, Laser-induced porous graphene films from com-
mercial polymers, Nat. Commun. 5 (2014) 1e8.
[29] M.K. Smith, D.X. Luong, T.L. Bougher, K. Kalaitzidou, J.M. Tour, B.A. Cola,
Thermal conductivity enhancement of laser induced graphene foam upon
P3HT infiltration, Appl. Phys. Lett. 109 (2016), 253107.
[30] Y. Li, D.X. Luong, J. Zhang, Y.R. Tarkunde, C. Kittrell, F. Sargunaraj, Y. Ji, C.J.
Arnusch, J.M. Tour, Laser-induced graphene in controlled atmospheres: from
superhydrophilic to superhydrophobic surfaces, Adv. Mater. 1700496en/a.
[31] Z. Peng, J. Lin, R. Ye, E.L.G. Samuel, J.M. Tour, Flexible and stackable laser-
induced graphene supercapacitors, ACS Appl. Mater. Interfaces 7 (2015)
3414e3419.
[32] Z. Peng, R. Ye, J.A. Mann, D. Zakhidov, Y. Li, P.R. Smalley, J. Lin, J.M. Tour,
Flexible boron-doped laser induced graphene microsupercapacitors, ACS
Nano 9 (2015) 1e17.
[33] L. Li, J. Zhang, Z. Peng, Y. Li, C. Gao, Y. Ji, R. Ye, N.D. Kim, Q. Zhong, Y. Yang, et
al., High-performance pseudocapacitive microsupercapacitors from laser-
induced graphene, Adv. Mater. 28 (2016) 838e845.
[34] R. Ye, Z. Peng, T. Wang, Y. Xu, J. Zhang, Y. Li, L.G. Nilewski, J. Lin, J.M. Tour, In
situ formation of metal oxide nanocrystals embedded in laser-induced gra-
phene, ACS Nano 9 (2015) 9244e9251.
[35] M. Schumann, R. Sauerbrey, M.C. Smayling, Permanent increase of the elec-
trical conductivity of polymers induced by ultraviolet laser radiation, Appl.
Phys. Lett. 58 (1991) 428e430.
[36] R. Srinivasan, R.R. Hall, W.D. Wilson, W.D. Loehle, D.C. Allbee, Ultraviolet laser
irradiation of the polyimide, PMDA-ODA (KaptonTM), to yield a patternable,
porous, electrically conducting carbon network, Synth. Met. 66 (1994)
301e307.
[37] A.C. Ferrari, J.C. Meyer, V. Scardaci, C. Casiraghi, M. Lazzeri, F. Mauri,
S. Piscanec, D. Jiang, K.S. Novoselov, S. Roth, et al., Raman spectrum of gra-
phene and graphene layers, Phys. Rev. Lett. 97 (2006) 1e4.
[38] M. Inagaki, L.-J. Meng, T. Ibuki, M. Sakai, Y. Hishiyama, Carbonization and
graphitization of polyimide film “novax”, Carbon N. Y. 29 (1991) 1239e1243.
[39] M. Inagaki, S. Harada, T. Sato, T. Nakajima, Y. Horino, K. Morita, Carbonization
of polyimide film “kapton”, Carbon N. Y. 27 (1989) 253e257.
[40] B.E. Scharfman, A.H. Techet, J.W.M. Bush, L. Bourouiba, Visualization of sneeze
ejecta: steps of fluid fragmentation leading to respiratory droplets, Exp. Fluids
57 (2016) 1e9.
[41] A. Ferrari, Raman spectroscopy of graphene and graphite, Solid State Com-
mun. 143 (2007) 47e57.
[42] Z. Sun, A.-R.O. Raji, Y. Zhu, C. Xiang, Z. Yan, C. Kittrell, E.L.G. Samuel, J.M. Tour,
Large-area bernal-stacked bi-, tri-, and tetralayer graphene, ACS Nano 6
(2012) 9790e9796.
[43] E.G. Gamaly, T.W. Ebbesen, Mechanism of carbon nanotube formation in the
arc discharge, Phys. Rev. B 52 (1995) 2083e2089.
[44] M. Kumar, Y. Ando, Chemical vapor deposition of carbon nanotubes: a review
on growth mechanism and mass production, J. Nanosci. Nanotechnol. 10
(2010) 3739e3758.