Nano Today 24 (2019) 81–102

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Review

Laser-derived graphene: A three-dimensional printed graphene

electrode and its emerging applications
Narendra Kurra a,∗,1 , Qiu Jiang a,1 , Pranati Nayak b,1 , Husam N. Alshareef a,∗
a
Materials Science and Engineering, Physical Science & Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal,
23955-6900, Saudi Arabia
b
Electrodics and Electrocatalysis (EEC) Biosensor Division, CSIR- Central Electrochemical Research Institute (CSIR-CECRI), Karaikudi, Tamilnadu, 630006,
India

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

Article history: Printing of binder-free graphene electrodes directly on substrates has the potential to enable a large
Received 6 October 2018 number of applications. Though conventional processing techniques such as ink-jet, screen-printing, and
Received in revised form 1 December 2018 roll coating methods offer reliable and scalable fabrication, device performance has often been limited by
Accepted 24 December 2018
re-stacking of the graphene sheets and by presence of passive binders and or additives. Laser-based, direct-
Available online 2 January 2019
write technologies have shown promise as a reliable, maskless, and template-free patterning method.
Thus, laser-derived graphene (LDG) electrode is emerging as a promising three-dimensional graphene
Keywords:
electrode that can be simultaneously derived from precursor carbons or polymers and patterned upon
Graphene
Laser writing
laser exposure. The LDG can be obtained through irradiation by a variety of laser sources including CO2
Energy infrared laser and femtosecond laser pulses, depending on the nature of the starting carbon precursors.
Sensor Controlling the microstructure, amount and types of doping, and post-deposition methods enable a vari-
Electrocatalysis ety of applications including energy storage, catalysis, sensing and biomedicine. In this review article, we
Electronics discuss recent progress in using laser-based fabrication of printed 3D graphene electrodes and its wide
spectrum of applications. The review also discusses the material aspects of 3D graphene electrodes and
provides an outlook for future potential.
© 2019 Elsevier Ltd. All rights reserved.

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
On-chip graphene electrodes by laser technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
Laser-derived 3D graphene electrodes for electrochemical energy storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
graphene-based symmetric supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
Fabrication of on-chip micro-supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
Asymmetric micro-supercapacitors based on Printed (on-chip) 3D Graphene Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
Effect of doping on electrochemical performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
On-chip biosensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
Heterogeneous electron transfer rates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .92
Electrochemical biosensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Nonenzymatic glucose detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
pH sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Electrocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Oxygen reduction/evolution reaction catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
HER catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96

∗ Corresponding authors.
E-mail addresses: [Link]@[Link] (N. Kurra),
[Link]@[Link] (H.N. Alshareef).
1
Equal contribution.

[Link]
1748-0132/© 2019 Elsevier Ltd. All rights reserved.
82 N. Kurra et al. / Nano Today 24 (2019) 81–102

Other exotic applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96

Antifouling properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Electroacoustic applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
Outlook and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100

Introduction from GO films in a single step [44]. It enabled simultaneous reduc-

tion of GO while generating desired electrode patterns in a scalable
Graphene has attracted significant attention from the research manner. The laser scribing technique facilitated controllable fabri-
community due to its fascinating physicochemical properties cation of 3D architectures from 2D stacked GO layers. Distinctively,
[1–10], making it suitable for a wide range of applications ranging Tour group pioneered the fabrication of graphitic carbon from com-
from nanoelectronics to energy storage [11–20]. High crystalline mercial polyimide through CO2 laser irradiation and extended this
quality graphene (e.g., graphene obtained through mechanical concept to a variety of natural and synthetic carbon precursors
exfoliation of the bulk graphite) is key to its superlative prop- [45]. This strategy offered direct formation of conductive and 3D
erties including massless ultrahigh mobility of charge carriers porous graphitic electrode patterns on insulating polymer sub-
(1̃05 cm2 /Vs) [21–25], high optical transparency (9̃7.7%) [26], strates, avoiding the additional step of processing the GO. Unlike
excellent thermal conductivity (5̃ kW/mK) [22], high mechanical using the mild source of the DVD burners for the laser reduction,
strength (1 Tpa) [12] and large theoretical surface area (2̃630 m2 /g) the CO2 laser is highly energetic and can transform natural carbon
[27]. Thermally-intensive processes, such as chemical vapor depo- sources into graphitic materials without the need for metal catalyst
sition (CVD) and thermal decomposition of silicon carbide, resulted layers. Since the laser converts carbon precursors into the graphitic
in the growth of high crystalline quality graphene with negligi- material, this technique is referred to as laser-induced graphene
ble defects [23,28–31]. However, the high thermal budget involved (LIG); a recent review article reports progress in this field [45]. The
in such processes limits the type of substrates that can be used noteworthy point here is that ‘graphene’ nomenclature was often
for direct growth of graphene, and often a transfer process is used for both LSG (laser-scribed graphene) and LIG (laser-induced
needed to make devices on substrates that cannot withstand high graphene), even though they are not a strictly single sheet of sp2
temperatures (e.g., plastic substrates). Therefore, rational design carbon lattice. The LSG and LIG terminologies have been used in the
and scalable processing of functional graphene materials at low literature reports, however, we propose the use of “laser-derived
temperatures on a variety of substrate platforms have attracted graphene (LDG)” as a generic term for the laser-based formation of
significant interest recently [10,20]. The trend toward developing printed graphene electrodes, independent of the laser type or pre-
cost-effective graphene materials enabled the ease of fabrication cursor material used. Such kinds of graphitic architectures may not
of functional sensors, electrocatalysts and energy storage devices have the same electronic quality as that of graphene obtained from
[4,14]. However, the bottleneck lies in the ‘restacking’ of graphene mechanical exfoliation or high-temperature growth methods, but
sheets through spontaneous van der Waals and ␲-␲ interactions in they are suitable for a variety of applications requiring printed pat-
a solution processable route [32], posing a challenge in developing terns of 3D graphene. Based on the laser conditions and the nature
graphene-based open frameworks. of carbon precursors, it is possible to control the microstructure,
Engineering native 2D graphene sheets into monolithic three- functionality, defect density and thus the associated properties of
dimensional (3D) porous architectures has become important LDG electrodes.
during the past decade due to the multitude of applications, In this article, we review recent progress on laser-derived 3D
including the fabrication of on-chip functional graphene devices. graphene electrodes and their emerging applications in the fields
Conventional CVD has been widely employed for making 3D of energy storage, electrocatalysis and sensing (Fig. 1). We start
graphene foams but lacks scalability due to the associated growth by summarizing the historical evolution of using laser-based tech-
process followed by etching of the metal scaffold [33]. In this sce- niques for the formation and direct patterning of graphene. We
nario, solution processing of functionalized graphene has become discuss both laser-induced reduction of GO to patterned graphene
attractive as it offers compatible coatings on a variety of sub- devices and laser-induced transformation of polymeric and other
strates in an inexpensive yet scalable manner [34]. Hummers’ natural carbon sources into 3D graphene architectures. We then
method typically relies on oxidation of bulk graphite powders, review the key lasing parameters and precursor that determine the
which enables a natural dispersion of graphene oxide (GO) sheets structure and properties of the resultant graphene patterns and the
with surface polarity and hydrophilicity [35]. Self-assembly of such versatile applications of LDG electrodes.
functionalized graphene materials enabled fabrication of 3D foam
structures; however, they suffer from the insulating nature of GO
[36,37]. To recover the electronic conductivity, a wide variety of On-chip graphene electrodes by laser technology
reduction protocols including chemical, thermal, and solvother-
mal were developed [3,16,38]. These reduction protocols were only The simultaneous formation and patterning of graphene on a
intended to reduce the GO; additional deposition and patterning substrate (SiO2 /Si, plastic, glass, and paper) is referred to as “on-
protocols should be adopted to fabricate on-substrate graphene chip graphene electrode” and is typically a binder-free monolithic
electrodes. Therefore, it is important to develop a strategy that architecture. Historically, the thermal atomic force microscope
involves simultaneous reduction, exfoliation, and printing of 3D (AFM) probe was employed to fabricate 1̃0 nm wide graphene
graphene electrodes into desired patterns on relevant substrates nanoribbons by local thermal reduction of GO [46]. The low-
for many potential applications [8,39–43]. throughput nature of AFM limited the scalability of this technique;
Laser scribing technology based on consumer-grade digital however, it could lead to the use of laser technology to make scal-
video disc (DVD) burners has shown significant promise as a solid- able graphene patterns. Laser technologies have been extensively
state approach for scalable fabrication of graphene-based devices employed in patterning and growth of nanostructured materials via
maskless and transfer printing routes [47,48]. For instance, Kurra
 N. Kurra et al. / Nano Today 24 (2019) 81–102 83

Fig. 1. Emerging electronics and electrochemical applications of laser-derived graphene architectures. Adapted with permissions from reference [65,69,70,72,73,81].

et al. employed pulsed laser interference ablation for direct pat- (wavelength = 788 nm, maximum power output = 5 mW) inside the
terning of graphite surfaces, which they then used as a source optical drive by pulsing through an objective lens. This technique
for obtaining graphene ribbons [49]. Laser processing was also is based on producing photothermal effects (the temperature may
employed for rapid synthesis of graphene structures in a catalyst- range from 300 to 500 ◦ C) through an IR laser beam to volatilize
free manner [50]. Pulsed laser sources were not only employed as the functional groups on the GO surface and produce conduc-
tools for patterning graphite surfaces but also used for reducing GO. tive reduced GO. This DVD LightScribe technique enabled selective
A variety of laser sources including femtosecond, nanosecond, Nd: reduction of GO without the need for a mask, which led to the
YAG, CO2 , diode, krF, and fiber types have been employed for reduc- fabrication of many graphene-based electronics and energy stor-
ing GO photothermally [51–64]. A focused laser beam provides age devices [44,65–68]. To demonstrate the complex patterning
highly controlled heating/cooling rates compared to conventional capability of LightScribe technology, intricate circuit designs were
annealing procedures, enabling rapid fabrication of graphene- sculpted on a man’s head by reducing GO film accordingly with
based devices. Concurrently, the high path length of the laser beam laser scribing (Fig. 1) [52,69–73]. This technique has the poten-
induces localized heating in selected areas with micron size preci- tial to create complex patterns without using masks, templates or
sion [45]. post-transferring protocols. Additionally, LSG-metal or LSG-metal
In 2012, Kaner et al. pioneered an inexpensive solid-state oxide composite structures were fabricated using this technology,
approach for reducing GO films using an ordinary DVD laser burner demonstrating the versatility in printing graphene and its com-
[65]. Commercial LightScribe drives are inexpensive (˜$20) and can posite electrodes directly on a substrate without using external
be controlled by a standard desktop computer. The LightScribe pro- masks.
gram allows control of the intensity or power of an IR laser beam
84 N. Kurra et al. / Nano Today 24 (2019) 81–102

Table 1
Summary of laser technologies used to produce graphene architectures from various carbon sources and their potential applications [44,52,54,63–65,72,74–88].

Carbon source Laser type Power Application References

788 nm, 5mW Supercapacitor [44,65]

Transistor
N/A (HP inc. 557S) Loudspeaker [79]
Photodetector
GO LightScribe DVD burner
788 nm, 5mW RRAM [82]
N/A (HP inc. 557S) Pressure sensor [80]
788 nm, 5mW LED [77]
788 nm, 5mW Earphone [81]
GO 650 nm laser 143 ␮W, 8.49 mm−1 Heater [86]
90 mW, 8.5 mm−1 Strain sensor [78]
GO 450 nm laser
0.13 mW, 7mm−1 Sound sensor [83,84]
248 nm UV laser 48-240 mJ/cm2
GO 788 nm CW laser N/A (HewlettePackard Inc.) N/A [63]
800 nm femtosecond laser 47-968 mJ cm−2
GO 650 nm laser 200 mW Photodetector [85]
GO 532 nm DPSS laser 5-80 mW, 50 ␮m s−1 N/A [88]
PI 450 nm Laser 500 mW, 8.5 mm−1 Intelligent throat [72]
PI, PEI 10.6 ␮m CO2 pulsed laser 2.4-5.4 mW, 3.5 inch s−1 Supercapacitor [52]
PI CO2 pulsed laser 6 mW Strain sensor [64]
SPEEK Ar–Kr laser, 514.5 nm 6 W, 500 mm−1 Supercapacitor [54]
Paper, coconut, bread, potato, etc. 10.6 ␮m CO2 pulsed laser 3.75 W, 15 cm s−1 N/A [74]
Teflon 9.3 ␮m CO2 pulsed laser 5 W, 15 cm s−1 N/A [76]
CH4 , H2 532 nm OPSS laser 5W N/A [87]
Wood 10.6 ␮m CO2 pulsed laser 7.8 W Electrocatalyst [75]

GO: graphene oxide; DVD: digital video disc; UV laser: ultraviolet laser; CW laser: continuous wave laser; DPSS laser: diode-pumped solid-state laser; OPSS laser: optically-
pumped solid-state laser; PI: polyimide; SPEEK: sulfonated poly(ether ether ketone); CH4 : methane; PEI: polyetherimide.

Lin et al. recently developed an innovative approach for writ- instance, the conductivity of GO film was enhanced by five orders
ing graphene patterns on commercial polyimide (PI, Kapton) films of magnitude (typical sheet resistance of GO films >20 M˝/sq
using a CO2 laser cutting tool usually found in machine shops [52]. to highly reduced GO films 8̃0 ˝/sq) through optimized lasing
This process is based on the photothermal transformation of sp3 conditions [44]. The phenomenon involves the release of oxygen-
carbon atoms into an sp2 carbon lattice by laser irradiation. In con- containing functional groups (CO, CO2 ) on instantaneous heating of
trast to an IR laser beam, the CO2 laser can produce temperatures GO film, with the subsequent expansion of stacked GO to expanded
>1000 ◦ C, which is responsible for graphitizing the polymer under graphene structure. The local pressure created by the liberated
ambient conditions, without the need for a metal catalyst. Further- gases causes protruded graphene morphology, which is evident in
more, this process was used to transform polysulfone membrane the SEM micrograph in Fig. 2a-d [44]. A very similar phenomenon
polymers into sulfur-doped LIG [71], demonstrating the versatil- occurs in the case of a polyimide substrate or thin polymeric films.
ity of this approach. By optimizing laser parameters and choosing Here, the viability of the CO2 laser to create localized temperatures
the appropriate gas environment, it was demonstrated that a vari- above 1000◦ C could induce graphitization at depths of a few tens of
ety of natural materials including wood, food, paper, and cardboard microns. The method involves the direct synthesis of graphene from
were transformed into LIG structures [74,75]. Fluorinated diamond polymeric substrates without requiring pre-synthesized GO (a typ-
and fluorinated graphene were recently synthesized from Teflon ical precursor material for LSG technology) and produces a highly
(polytetrafluoroethylene) via laser-induced transformation [76]. conductive graphene scaffold (sheet resistance 10–100 ˝/sq) [52].
Table 1 summarizes the laser-based technologies that have been Since the quality of graphene formed by direct laser irradiation
used for producing graphene-based patterns either from GO, poly- influences the device performance, it is crucial to investigate the
mers or natural resources and their wide range of applications morphology, electrical conductivity, surface functionality, specific
[44,52,54,63–65,72,74–88]. surface area, and chemical nature. The instantaneous heating and
In this review article, we emphasize two types of direct-write simultaneous release of gaseous byproducts turn both GO- and PI-
laser technologies that can be used to generate 3D graphene elec- derived graphene into a highly porous 3D electrode rich in edge
trode patterns directly on substrates: (i) conversion of GO into plane sites, as depicted in Fig. 2a-d. The quality and defects of
conductive reduced GO using an IR laser similar to those found graphitic carbon can be quantified using Raman analysis (Fig. 2e,
in DVD technologies, and (ii) conversion of polymers and natu- f). Raman spectroscopy is one of the most sensitive and informa-
ral carbon sources into graphitic carbon using a CO2 laser. These tive techniques to characterize disorder in the sp2 carbon lattice.
two laser techniques share common aspects that offer direct-write In graphene-based materials, the Raman spectrum predominantly
(maskless) fabrication of printed 3D graphene electrodes. In the fol- consists of three peaks which are referred to as D, G, and 2D bands
lowing sections, we discuss progress on the formation of these 3D [89–91]. The extent of the reduction of GO after laser irradiation
printed graphene electrodes and their applications in carbon elec- can be inferred from the position, shape, full width at half maxima
tronics, electrochemical capacitors, sensors, electrocatalysts and (FWHM) and the ratio of the peaks with respect to the GO. The D
bio-medical applications (Fig. 1). band originates from the breaking of the translational symmetry
The unique aspect of the laser technique is the photothermal of the sp2 carbon lattice, the G band from the stretching vibra-
conversion or transformation of nonconductive carbon materials tion of the sp2 carbon lattice, and the 2D band from the stacking
into conductive graphitic structures. The laser power is determined of graphene sheets along c-axis. ID /IG ratio can be used to estimate
by the type of laser, spot size and other instrumental parameters the defect density and the shape of the 2D band reveals the nature
that can control the localized temperature profiles. The instanta- of the stacking of graphene sheets. The narrow D and G bands after
neous temperature rise in the lasing area influences the choice laser exposure of GO and the appearance of the 2D band indicates a
between the molecular and atomic structure of the carbon. For significant reduction of GO into the graphitic structure with c-axis
 N. Kurra et al. / Nano Today 24 (2019) 81–102 85

Fig. 2. SEM micrographs of (a) LSG and (b) LIG. Corresponding magnified cross-sectional SEM images are shown in (c) and (d). Raman spectra are presented in (e) and (f),
respectively. GO: graphene oxide, LSG: laser-scribed graphene, PI: polyimide, LIG: laser-induced graphene. Adapted with permissions from reference [44,52].

periodicity (Fig. 2e). As detailed in a recent review article, insight Laser-derived 3D graphene electrodes for electrochemical
into GO reduction by laser irradiation was analyzed and quanti- energy storage
fied using infrared, X-ray photoelectron and UV–vis spectroscopies
[92]. The Raman spectrum of graphene derived from polyimide dis- The rapid growth in miniaturized electronics and self-powered
played intense and narrow peaks corresponding to the D, G, and 2D sensors demands the development of small-scale energy storage
bands, confirming that polyimide transforms into graphene under units [93]. For instance, implantable biochips, radio frequency iden-
CO2 laser irradiation. The degree of graphitization can be controlled tification (RFID) tags, environmental sensors, nanorobotics and
by the appropriate choice of laser power [52]. Since a CO2 laser pro- microelectromechanical systems (MEMs) need compatible micro-
duces higher temperatures compared to a DVD burner, the degree power sources [93,94]. In addition, the energy autonomy requires
of graphitization is superior in the former. Other natural carbon the development of harvesting units to transform intermittent
sources such as bread, coconut shell and wood were graphitized renewable sources, such as solar, wind and thermal, into a contin-
using the right choice of CO2 laser parameters and environments. uous power supply over prolonged periods for “self-sufficiency”.
The key features of the LDG include a porous conductive scaf- On-chip energy storage is the advanced version of electrochem-
fold with abundant defect sites, which is beneficial for efficient ical energy storage to cope with miniaturized electronics. Thin
transport of electrolyte ions and electrons. This makes it an excel- film batteries and micro-batteries have been commercialized, but
lent printed 3D electrode for electrochemical applications. It is they suffer from limited lifetime and low power density [95–97].
noteworthy that these LDG electrodes do not require any binders Since micro-supercapacitors offer an essentially infinite lifetime
for electrochemical applications. Such binders can block some of with higher power density than micro-batteries, they are suited
the electrochemical sites and influence the intrinsic electrochem- for applications including remote sensing networks, implantable
ical properties of carbon-based materials. Thus, the laser-formed sensors and the internet of things (IoT) [94]. In such devices, the har-
printed graphene electrodes could offer a significant advantage in vested energy may be intermittent while providing non-constant
electrochemical applications. In the following sections, we review voltage output with time [98]. Since batteries often require con-
several applications that capitalize on the advantages of printed 3D stant voltage output for charging, micro-supercapacitors can be
graphene electrodes to improve electrochemical performance over charged more efficiently by drawing the maximum current supply
re-stacked graphene layers. from the source, irrespective of voltage output [98,99].
86 N. Kurra et al. / Nano Today 24 (2019) 81–102

Fig. 3. Laser-derived graphene electrodes for electrochemical capacitors. (a) A cross-sectional view presenting the LSG electrodes supported on a flexible substrate. (b)
Impedance plot of an LSG sandwich supercapacitor in 1 M H3 PO4 . (c) Comparison of stack capacitance of LSG supercapacitors in aqueous and gel electrolytes. Adapted
with permission from reference [44]. Copyright 2012, American Association for the Advancement of Science. (d) Stackable series and parallel connected LIG solid-state
supercapacitors. (e) Charge-discharge profiles of single and series connected LIG supercapacitors. Adapted with permission from reference [113]. Copyright 2015, American
Chemical Society.

The typical layout of a micro-supercapacitor may include either Initial efforts have been focused on synthesis of graphene oxide,
thin film or planar interdigitated electrode architecture, but the and ways to reduce it for electrochemical energy storage appli-
latter has advantages such as faster electrolyte ion movement, cations [110–112]. Kaner’s group pioneered the process of GO
high power and rate capabilities, and easier on-chip integration reduction by laser scribing graphene electrodes using a standard
[100,101]. LightScribe DVD optical drive method [44]. Their work illustrated
The field of micro-supercapacitors is evolving rapidly [102]. that irradiation of GO film with an IR laser resulted in mechani-
As far as the materials are concerned, carbon is earth- cally robust and electrically conducting (17.4 S/cm) films with a
abundant and cheap; various nanostructured carbon materials specific surface area of 1520 m2 /g. They used this approach to fab-
have thus been explored as micro-supercapacitor electrodes. Acti- ricate a printed flexible electrochemical capacitor without binders
vated carbon, onion-like carbon, carbide-derived carbons, carbon or current collectors (Fig. 3a). They optimized laser parameters to
nanotubes, and graphene were employed in fabricating micro- achieve lower equivalent resistance values in their LSG superca-
supercapacitors [103–107]. Various pseudocapacitive electrode pacitors (Fig. 3b). Furthermore, their supercapacitors delivered a
materials including transition metal oxides, nitrides, carbides and power density of 2̃0 W/cm3 , which is almost 20 times higher than
conducting polymers have also been explored. There are excellent activated carbon-based supercapacitors. As illustrated in Fig. 3c,
review articles describing the progress on micro-supercapacitors the flexible solid-state supercapacitors were made using poly(vinyl
[94,95,101,102,108,109]. Most of the micro-supercapacitors were alcohol)-phosphoric acid (PVA/H3 PO4 ) gel electrolyte, which gave
fabricated using standard microfabrication methods, which involve a similar electrochemical performance to that of liquid electrolyte.
a multi-step protocol and expensive infrastructures such as a This is mostly because of the porous LSG electrode structure, which
mask aligner and a sophisticated cleanroom. Therefore, direct and allowed the gel electrolyte to penetrate deep into the electrode.
scalable fabrication of micro-supercapacitors with minimal infras- Peng et al. demonstrated vertically stacked graphene superca-
tructure is a requirement for low-cost solutions. pacitors by transforming both sides of polyimide sheets into porous
graphene through laser irradiation [113]. The advantage of this fab-
rication method is that the 3D graphene electrodes can be produced
graphene-based symmetric supercapacitors under ambient conditions in which the remaining PI layer at the
middle separates the graphene electrodes, enabling the fabrication
Gao et al. employed a laser technique to selectively write of vertically integrated supercapacitors to enhance the volumetric
reduced GO patterns directly on GO free-standing film [51]. The electrochemical performance while preserving the device flexibil-
laser-reduced GO was used to form an electrode material pattern, ity (Fig. 3d). These supercapacitors can be integrated into series
while the hydrated GO served as an ionic conductor in fabricating and parallel connections to meet the required power ratings. Com-
planar graphene electrochemical capacitors. However, the electri- pared to single devices, series connected micro-supercapacitors
cal and ionic conductivities were not sufficiently high, causing poor exhibit three times higher voltage window (Fig. 3e), demonstrat-
frequency response and large internal resistance (6.5 k) of the ing the ability of the laser technique to manufacture integrated
as-made graphene devices with GO as an ionic conductive medium.
 N. Kurra et al. / Nano Today 24 (2019) 81–102 87

Fig. 4. (a-c) Schematic illustrating the fabrication of an LSG micro-supercapacitor. (d) Phase angle versus frequency of LSG MSC in comparison to electrolytic and activated
carbon-SCs. (e) Ragone plot comparing the electrochemical performance of LSG micro-supercapacitors with the state-of-the-art Li thin film batteries and electrolytic capac-
itors; the inset displays potential scalability of the laser scribing technique in producing more than 100 devices in a single run. Adapted with permission from reference [65].
Copyright 2013, Springer Nature.

graphene-based supercapacitors according to the need for output activated carbon supercapacitors and approaching electrolytic
current/voltage ratings. capacitor performance (Fig. 4 d). Laser scribing technology has
enabled an expanded open structure of graphene in which the
distributed nature of the charge can be minimized, unlike in the
Fabrication of on-chip micro-supercapacitors
case of microporous carbon electrodes. Furthermore, LSG MSCs
delivered higher energy density at high charge-discharge rates
Laser techniques allow planar fabrication of graphitic
than state-of-the-art micro-supercapacitors (Fig. 4e).
electrodes, enabling the direct fabrication of LDG micro-
Li et al. employed a femtolaser-reduction process to pattern both
supercapacitors. EI-Kady et al. have demonstrated the scalable
rGO electrodes and Au current collectors in a single step to improve
fabrication of graphene micro-supercapacitors over large areas by
the conductivity of rGO electrodes [100]. Unlike continuous wave
direct laser writing on GO films using a standard LightScribe DVD
lasers, femtosecond lasers can induce multiphoton polymerization,
burner [44,65]. They fabricated flexible micro-supercapacitors
reduction, melting and etching of different categories of materials.
for powering up flexible electronics but also showed promise
For instance, the strong peak power of ultrashort pulses enables
for on-chip integration with Microelectromechanical systems
a nonlinear multiphoton interaction with the materials within the
(MEMS) or complementary metal-oxide-semiconductor(CMOS)
focal point, which may be beneficial for obtaining composites of
technologies. The laser scribing method offered the fabrication
rGO. In this study, hydrated GO and chloroauric acid nanocompos-
of a single device in 18 s. As illustrated in Fig. 4a-c, the direct
ite film was reduced in-situ by exposing them to the femtosecond
‘writing’ technique does not require masks and can be done in a
laser beam to create rGO/Au micropatterns. The conductivity of
regular laboratory environment without the need for a clean room.
rGO/Au (1100 S/cm) was improved by two orders of magnitude
The presence of a GO layer in the interspaces between reduced
compared to rGO alone, resulting in improved rate capabilities (vol-
GO serves as a separator and electrolyte (provided with enough
umetric capacitance of 10.2 F/cm3 at high scan rate of 100 V/s) and
ionic conductivity) for the all-carbon micro-supercapacitor. They
power densities (time constant of 2.76 ms) over rGO-based micro-
also fabricated an array of micro-supercapacitors (>100) on a
supercapacitors fabricated by the femtosecond laser technique.
single piece of GO film deposited on a DVD. A lateral spatial
Hwang et al. demonstrated the synthesis and processing of
resolution of 2̃0 ␮m was demonstrated using this LightScribe
LSG/RuO2 nanocomposite electrodes through laser-induced redox
method. Remarkably, these micro-supercapacitors exhibited
reactions between precursors, GO and RuCl3 [67]. This approach
three times higher energy and 200 times higher power compared
enabled the single-step fabrication of binder-free, metal current-
to commercial activated carbon supercapacitors. These devices
collector-free graphene/RuO2 interdigitated electrodes. The laser
even exhibited higher power density than micro-batteries and
technique has also enabled the fabrication of integrated devices
higher energy density than electrolytic capacitors. Higher power
in series and parallel configurations to meet required power rat-
densities could likely be achieved by reducing the ion-diffusion
ings. The laser scribing tool thus offers flexibility in fabricating
pathways through the selection of smaller width and spacing
hybrid graphene electrodes through the pre-selection of desired
between the micro-electrodes. It is evident that the phase angle
GO-composite material.
response of LSG MSCs is far better than that of commercial
88 N. Kurra et al. / Nano Today 24 (2019) 81–102

Fig. 5. (a) Schematic illustration for laser writing of 3D graphene patterns on lignin surface via lift-off in a water bath for micro-supercapacitor fabrication. (b) Digital
photograph of the micro-supercapacitor on polycarbonate (PC) substrate. (c) Raman spectra presenting the dependence of laser parameters on the nature of the graphitic
carbon produced. (d) Cyclic voltammograms of an optimized LDG micro-supercapacitor. (e) Comparison of corresponding electrochemical performance of LDG MSCs fabricated
using different laser powers. Adapted with permission from reference [114]. Copyright 2018, Wiley-VCH.

Zhang et al. recently demonstrated laser lithography on lignin, times through optimized graphitic carbon electrodes. Importantly,
which is an abundant natural polymer that exists in plants all these LDG devices displayed rate capabilities up to 100 V/s,
(Fig. 5a,b) [114]. Lignin is generally considered to be useless plant which is likely useful for high rate applications. The versatility and
extract but transforming it into a useful product has both envi- environmental friendliness of lignin laser lithography can inspire
ronmental and commercial significance. Laser conditions were both the fabrication of graphene-based MSCs and the sustainable
optimized to convert lignin film into conductive graphitic patterns utilization of lignin.
followed by lift-off in water to remove unexposed lignin regions
(Fig. 5c). The electrochemical performance of LDG electrodes was Asymmetric micro-supercapacitors based on Printed (on-chip) 3D
then compared in a symmetrical configuration, as illustrated in Graphene Electrodes
Fig. 5d and 5e. These symmetric devices displayed areal capacitance
values in the range of 3–10 mF/cm2 at a scan rate of 10 mV/s, indi- Aqueous symmetric supercapacitors have a limited cell voltage
cating that the capacitance values can be raised as much as three (<1 V), necessitating the development of a high operating voltage
 N. Kurra et al. / Nano Today 24 (2019) 81–102 89

Fig. 6. LDG-based asymmetric micro-supercapacitors. (a) Selective electrodeposition of MnO2 nanoparticles on an LSG scaffold. (b) Progressive cyclic voltammograms
illustrating the 2 V voltage window of LSG/MnO2 //LSG device. Adapted with permission from reference [66]. Copyright 2014, National Academy of Sciences. (c) Fabrication
of all-pseudocapacitive micro-supercapacitor by selective electrodeposition of electroactive materials. (d) Cyclic voltammograms of the asymmetric MSC (voltage window
of 1.8 V) at different scan rates. Adapted with permission from reference [116]. Copyright 2015, Wiley-VCH.

window. One approach to achieve this is through the asymmetric was estimated to be 21.9 m F/cm2 and 5.4 F/cm3 respectively, at
design of electrodes [115,116]. In this type of device, the com- a current density of 0.25 mA/cm2 . These values resulted in areal
plementary potential windows of positive and negative electrode and volumetric energy/power performance (Maximum EA = 9.6
materials add up to increase the operating voltage. Since the energy ␮Wh/cm2 and EV = 2.4 mWh/cm3 ; Maximum PA 11564 ␮W/cm2
density of the device is determined by its capacitance and the and PV = 2891 mW/cm3 ), which is superior to symmetric devices.
square of the working voltage (E=CV2 /2), the effect of enlarging the Moosavifard et al. developed similar asymmetric 3D
voltage window is significant. The fabrication of asymmetric micro- LGS/CoNi2 S4 //LSG MSCs by laser scribing followed by selec-
supercapacitors by conventional photolithography involves at least tive electrodeposition [117]. 3D graphene not only provides
a two-step lithography process and the use of a special photomask. current collecting pathways for the electrons but also high surface
However, LDG patterns enable direct and selective deposition of area support for the direct growth of NiCo2 S4 . These asymmetric
the right choice of materials in designing asymmetric MSCs in a devices displayed a stable operating voltage window of 1.7 V,
single step. which is higher than the conventional activated carbon symmetric
EI-Kady et al. demonstrated the scalable fabrication of capacitors in aqueous electrolytes (0.8–1 V). Device volumetric
graphene-based asymmetric micro-supercapacitors using stack capacitance up to 112.4 F/cm3 was achieved with an energy
“top-down” LightScribe lithography and “bottom-up” selec- density of 49 Wh/L. This is comparable to those of packaged lead-
tive electrodeposition. Positive LSG-MnO2 and negative LSG acid battery cells. These studies proved the potential of the 3D
electrodes were employed in designing an asymmetric 3D conductive LDG platform to develop hybrid electrodes and hybrid
micro-supercapacitor (Fig. 6a). As illustrated in Fig. 6b, the LSG- on-plastic energy storage devices. Table 2 summarizes the elec-
MnO2 //LSG 3D asymmetric micro-supercapacitor operated at trochemical performance of various LDG-based supercapacitors in
a voltage window of 2 V while exhibiting a volumetric stack literature [44,51,52,65–67,100,113,114,116–120].
capacitance of 250 F/cm3 , which is higher than state-of-the-art
carbon MSCs (<5 F/cm3 ). The array of compact hybrid LSG-MnO2
3D MSCs was integrated with solar cells to demonstrate efficient Effect of doping on electrochemical performance
solar energy harvesting and storage [66].
Li et al. demonstrated the fabrication of all-solid-state, flexible To improve the electrochemical performance of graphene-based
asymmetric MSCs by electrochemical deposition [116]. Pseudoca- materials, various strategies have been employed to tune the elec-
pacitive materials were electrodeposited on the LIG fingers. LIG tronic band structure. Among them, heteroatom doping including
not only works as an electrical double layer electrode but its boron, nitrogen, phosphorous and sulfur is known to be an active
conductive nature enabled the electrodeposition of pseudocapac- area of research. For instance, p-type doping by boron atoms into
itive materials such as MnO2 , FeOOH, and polyaniline (PANI) to the carbon lattice can shift the Fermi level toward the valence band,
form LIG-MnO2 , LIG-FeOOH, and LIG-PANI composites, respectively causing enhancement in charge storage and transfer within the
(Fig. 6c). An asymmetric MSC was fabricated by employing LIG- doped graphene structure. Heteroatom doping can also contribute
FeOOH as a negative electrode and LIG-MnO2 as a positive electrode additional pseudocapacitance and thus improve the overall elec-
(LIG-FeOOH//LIG-MnO2 ). When tested in PVA/LiCl electrolyte, the trode capacitance. Peng et al. demonstrated the direct fabrication of
asymmetric device displayed a voltage window of 1.8 V (Fig. 6d). B-doped porous graphene micro-supercapacitors [118]. They incor-
The areal and volumetric capacitance of the full asymmetric device porated boric acid into polyimide sheets followed by laser-based
transformation and patterning simultaneously. Similarly, Guo et al.
90 N. Kurra et al. / Nano Today 24 (2019) 81–102

Table 2
Summary of LDG-based supercapacitors reported in literature.

Type Design Configuration Electrolyte Voltage CA CV EV PV References

(V) (mF/cm2 ) (F/cm3 ) (mWh/cm3 ) (W/cm3 )

GO→rGO (22 ␮m) In-plane Symmetric 1 M Na2 SO4 1 1.2 N/A 1 100 [51]
1 M H3 PO4 1 3.67 0.4 0.04 1
PVA/H3 PO4 1 N/A 0.4 0.04 1
GO→LSG (68.2 ␮m) Sandwich Symmetric [44]
tetraethylammonium 3 4.82 N/A 0.4 1̃0
tetrafluoroborate
EMIMBF4 4 5.02 N/A 1 1̃0
GO→LSG (7.6 ␮m) In-plane Symmetric PVA/H2 SO4 1 2.3 2.35 N/A 200 [65]
1 M H2 SO4 1 3.5 1.5 0.3 50
PI→LIG (25 ␮m) In-plane Symmetric [52]
BMIM-BF4 3.5 2 0.8 1 100
PI/H3 BO3 →B doped LIG In-plane Symmetric PVA/H2 SO4 1 16.5 6 0.3 1 [118]
(25 ␮m)
GO→LSG + ED (MnO2 ) In-plane Asymmetric 1 M Na2 SO4 0.9 400 250 30 1 [66]
GO/RuCl3 →LSG/RuO2 In-plane Symmetric 1 M H2 SO4 1 70 158 1 1 [67]
(25 ␮m)
PI→LIG (25 ␮m) Sandwich Symmetric PVA/H2 SO4 1 9 N/A 0.2 1 [113]
GO/HAuCl4 →rGO/Au Nps In-plane Asymmetric PVA/H2 SO4 1 0.77 17.2 N/A N/A [100]
(13.7 ␮m)
PI→LIG + ED In-plane Asymmetric PVA/LiCl 1.8 21.9 5.4 3.2 2.89 [116]
(FeOOH(41 ␮m//MnO2 (101 ␮m))
GO→rGO + ED (CoNi2 S4 ) In-plane Asymmetric PVA/KOH 1.7 N/A 122.4 49 1̃0 [117]
PI→LIG (80 ␮m) In-plane Symmetric PVA/H2 SO4 1 22.4 2.8 N/A N/A [119]
PI→LIG In-plane Symmetric PVA/H2 SO4 1 1̃0 N/A N/A N/A [120]
Lignin→LIG In-plane Symmetric PVA/H2 SO4 1 25.1 6.27 1 2 [114]

GO: graphene oxide; PI: polyimide; PVA: polyvinyl alcohol; LSG: laser-scribed graphene; LIG: laser-induced graphene; ED: electrodeposition.

prepared reduced GO with 10 wt% of nitrogen doping by using fem- carbon composed of nanodomains of graphene layers showed
tosecond laser irradiation [121]. Recently, Fu et al. achieved 8 wt% of promise as a reversible Na-ion anode but suffered from the lim-
nitrogen doping by using CO2 laser reduction of graphite oxide con- itations of Na-plating issues at higher current densities. As such,
taining nitrogen-rich carbon nanoparticles [122]. These approaches the trend toward developing conductive carbon anode materials
are based on simultaneous reduction and doping of GO and showed is highly desired for high rate Na-ion storage. Developing open
improvement in electrochemical performance when compared to architectures of graphitic materials with expanded structures in
undoped graphene electrodes. a self-standing manner are important for stable and high rate elec-
As illustrated in Fig. 7, Peng et al. employed boric acid mixed trochemical storage of Na-ions.
polyamic acid solutions (solvent: N-methylpyrrolidone) as a PI pre- Zhang et al. employed a novel strategy based on the single-step
cursor film. Different weight percentages of boric acid (H3 BO3 ), laser-induced transformation of urea-containing polyimide into an
1–8 wt% relative to PAA, were mixed and bath sonicated for 30 min expanded 3D graphene anode, with simultaneous doping of high
to form a uniform precursor solution [118]. Condensation of the concentrations of nitrogen (1̃3 at%) [124]. The versatile nature of
precursor solution produced a boric acid-containing polyimide. The this laser process enabled direct bonding of the 3D graphene anode
laser transformed H3 BO3 -PI into B-LIG patterns, as illustrated in to the current collectors without the need for binders or conduc-
Fig. 7a. The preference of boric acid over other boron precursors is tive additives. This presents a clear advantage over chemical or
based on the ease of dehydration and polymerization upon thermal hydrothermal methods (Fig. 8a). A very thin layer of PI (which need
treatment. not be continuous) could act as a glue that improves adhesion of
The electrochemical performance of B-LIG with different ini- LDG to Cu surface. The ohmic contact between the Cu and graphitic
tial H3 BO3 loadings was compared. PVA/H2 SO4 gel electrolyte was material can be confirmed from the electrochemical response,
coated onto the interdigitated electrodes with Kapton tape sealing where interfacial impedance between the two can be measured.
to avoid touching the Ag paint at the edges for contact purposes By optimizing the laser parameters and surface pre-treatments of
(Fig. 7b). Among all the devices, 5B-LIG-MSC exhibited higher cur- Cu and Ni foams, it is possible to grow graphitic carbon from poly-
rent values in CV curves at the same scan rate, confirming the imide precursors coated on those substrates. Since carbon has high
highest areal capacitance (Fig. 7c). The increase of boron doping solubility in Ni matrix, it is expected that graphitic carbon growth
from 0 to 5 wt% raised the areal capacitance by four times compared on Ni foam substrates may be feasible as well. Such strategy can be
to undoped LIG. They hypothesized that the optimal boron doping used to fabricate 3D porous graphitic electrodes for a variety of elec-
in LIG improves the capacitance by increasing the hole charge den- trochemical applications. This study compared the electrochemical
sity and thus enhances the charge storage. The areal capacitance of storage of Na-ions of LSG electrodes: (i) LSG without nitrogen dop-
corresponding devices reached up to 16.5 mF/cm2 , which is three ing (LSG), (ii) nitrogen doping in the air (NLSG-1) and (iii) nitrogen
times higher than undoped LIG devices, with concomitant energy doping in a nitrogen environment (NLSG-2). The NLSG-2 electrode
density increasing by 5–10 times. However, higher levels of boron exhibited an initial coulombic efficiency (CE) up to 74% (Fig. 8b),
doping beyond 5 wt% might induce more scattering sites for the which exceeds that of most reported carbonaceous anodes, such
electrons in the LIG sheets, causing the diminished conductivity as hard and soft carbon [124]. In addition, Na-ion capacities up to
values and thus diminished capacitance. 425 mAh g−1 at 0.1 A g−1 were achieved with excellent rate capa-
The effect of nitrogen doping into LDG electrodes on the elec- bilities. A capacity of 148 mA h g−1 at a current density of 10 A g-1
trochemical storage of Na-ions was recently investigated. Bulk was also obtained with excellent cycling stability (Fig. 8c). These
graphite has been widely employed as a stable and robust anode results open a new path for the fabrication of high-performance 3D
material for commercial Li-ion battery technology today [123]. graphene anodes directly on current collectors for Na-ion battery
However, graphite cannot intercalate large Na-ions, posing a chal- anodes that can be optimized to work as well for K-, Mg and Al-
lenge in developing robust and high capacity Na-ion anodes. Hard batteries. The ability to tune up the electrochemical properties of
 N. Kurra et al. / Nano Today 24 (2019) 81–102 91

Fig. 7. Fabrication of B-doped LIG micro-supercapacitors (B-LIG-MSC). (a) (i) Mixing of polyamic acid with H3 BO3 solution, (ii) condensing into PI/H3 BO3 sheet, (iii) laser-
induced transformation into boron-doped porous graphene patterns. (b) Flexible solid-state B-LIG micro-supercapacitor in gel electrolyte. (c) Comparing the electrochemical
performance of LIG micro-supercapacitors with different amounts of boron loadings. Adapted with permission from reference [118]. Copyright 2015, American Chemical
Society.

Fig. 8. (a) Schematic illustrating the process flow used to fabricate the nitrogen-doped 3D graphene directly onto Cu foil through laser irradiation. (b) CV curves of NLSG-2
electrodes (at 0.1 mV s−1 ). (c) Rate performance of LSG, NLSG-1 and NLSG-2 electrodes at different current densities. LSG: laser-scribed graphene from polyimide. NLSG-1:
Urea containing PI; LSG is formed in the air. NLSG-2: Urea containing PI; LSG was formed under a nitrogen environment. Adapted with permission from reference [124].
Copyright 2018, Wiley-VCH.

LDG electrodes through doping strategies is compelling. Such dop- cal surface area for metal ions adsorption/insertion compared to
ing strategies could lead to exploring high rate LDG-based energy restacked layered materials, they are better electrodes for capaci-
storage devices. Since LDG electrodes offer higher electrochemi- tive storage applications. LDG electrodes should also be explored
92 N. Kurra et al. / Nano Today 24 (2019) 81–102

Fig. 9. (a) Three-electrode patterned LSG (from GO) electrodes. (b) Cyclic voltammograms of 1, 1 -ferrocene methanol at a scan rate of 10 mV s−1 at EPPG electrode surfaces
compared to the LSG system. Adapted with permission from reference [137]. Copyright 2014, Royal Society of Chemistry. (c) Digital photograph showing scalable fabrication
of LSG (from PI) electrode arrays (the projection displays the scheme of a single 3-electrode pattern on the PI sheet and a cross-sectional SEM micrograph of LSG). (d)
Differential pulse voltammetry scans of LSG and Pt/LSG electrodes (vs. Ag/AgCl) in 0.1 M PBS (pH 7.0) containing 1 × 10−3 M AA + 40 × 10−6 M DA + 40 × 10−6 M UA. Adapted
with permission from reference [73]. Copyright 2015, Wiley.

for electrochemical storage of different metal cations. Further, laser sensor prototype on GO film by laser scribing (Fig. 9a) [137].
parameters should be optimized to produce porous carbon type The LSG electrode demonstrated a fast heterogeneous electron
cathode materials for metal adsorption. Hence, we expect that laser transfer rate (k◦ ) of 0.02373 cm s−1 for the potassium ferricyanide,
processing can be a promising route for the fabrication of in-plane K3 [Fe(CN)6 ] redox mediator. This exceeds the highly relevant
metal-ion capacitors via optimized laser conditions [125]. carbon alternatives such as edge plane pyrolytic graphite, EPPG
(k◦ = 0.022 cm s−1 ), and basal plane pyrolytic graphite, BPPG
On-chip biosensors (k◦ = 10-9 cm s−1 ) [138,139]. This stand-alone prototype displayed
intrinsic electrochemical properties without the summative effects
Electrochemical sensing has long been recognized as a promis- in the case of powdery electrodes (Fig. 9b). This technique offers
ing technique for the detection of biologically significant molecules, free-standing 3D graphene electrode architecture while avoiding
but stringent demands exist on sensor performance. These include the external binders and additives – a new step away from the
high sensitivity, selectivity, fast response besides fairly low cost fab- conventional powdery electrodes. However, as mentioned, the
rication [126]. Carbon electrodes have become attractive for this preparation protocol involves a multi-step technique involving the
type of sensor applications due to their electronic conductivity, preparation of GO, casting of GO on a DVD drive and finally scribing
chemical robustness in electrolyte media and efficient charge trans- with LightScribe technology. The quality of graphene produced
fer for a wide variety of analytes [127]. Due to its 2D morphology, is thus highly dependent on the quality of GO (mainly due to
graphene has been a favored platform for electrochemical sensing oxygen functionalities in LSG, which influences electrochemical
applications. The key concepts of the electron transfer rate and ana- behavior) and cannot be controlled by an external laser source
lytical performance in graphene-based sensors are governed by the (here a LightScribe DVD drive).
combined effects of the specific surface area, electronic conductiv- The issues caused by the complicated multi-step fabrication
ity and available edge plane sites [128–130]. procedure were avoided by the single-step fabrication of a sen-
sor prototype by direct laser-induced transformation of a PI sheet
under ambient atmosphere (Fig. 9c, d) [73]. These electrodes dis-
Heterogeneous electron transfer rates played a fast HET rate (k◦ ) of 0.1150 and 0.0868 cms−1 for both
inner-sphere and outer-sphere redox mediators, [Fe(CN)6 ]4− and
Graphene-based electrochemical sensing platforms often [Ru(NH3 )6 ]3+ respectively, which is significantly better than other
employ chemically made graphite oxide that is subsequently types of graphene-based platforms. The k◦ value was further
reduced by chemical, electrochemical, thermal or hydrothermal enhanced by selective anchoring of Pt nanoparticles over LSG and
routes [131–135]. However, electrodes processed through the is comparable to many other graphenes obtained through different
above methods tend to be difficult for integration as practical routes and commercial pyrolytic graphite-based electrodes (illus-
devices. This is due to the requirement of additives, fillers and trated in Table 3) [73,137–141]. These PI-derived LSG electrodes
polymeric binders for coatings. This introduces many drawbacks, exhibit significantly improved electrocatalytic activity in the oxi-
such as the reduction of the specific surface area, electronic dation of ascorbic acid (AA), dopamine (DA) and uric acid (UA) with
conductivity and charge transfer rate due to the inherent layer enlarged peak separations (EAA–DA = 234 and 236 mV, EDA–UA =
restacking nature of graphene during the solution processing 134 and 143 mV and EAA–UA = 368 and 379 mV) for LSG and Pt/LSG
[136]. Therefore, fabricating graphene-based devices while getting respectively. The detection of these biomarkers was consequently
rid of the above detrimental effects is highly important for elec- achieved with high sensitivity and selectivity in a wide concentra-
trochemical sensing applications. The first step in this direction tion range. This is ascribed to the binder-free 3D porous network of
was developed by the Kaner group, who designed a graphene
 N. Kurra et al. / Nano Today 24 (2019) 81–102 93

Fig. 10. (a) Schematic depicting electrochemical thrombin detection mechanism using LSG. (b) Change of the DPV peak current at varying thrombin concentration in serum.
Adapted with permission from reference [143]. Copyright 2017, American Chemical Society. (c) Laser fabrication of paper-based analytical devices. (d) Picric acid detection
using differential pulse voltammograms with the presence of 0.48, 0.91, 1.30, and 2.0 mmol L−1 picric acid (solid curves) and 0.1 mol L−1 PBS (pH 2.0). Adapted with permission
from reference [144]. Copyright 2017, Wiley.

Table 3
HET rate (k◦ ) of two redox mediators using different graphitic electrode materials.

k◦ (cm/s)
Electrode References
[Fe(CN)6 ]4− [Ru(NH3 )6 ]3+

Pt/LSG LSG 0.28230.1150 0.2312 0.0868 [73]

BPPG EPPG 10−9 0.022 0.00380.00877 [138,139]
L-graphene 0.02373 – [137]
CVD-Gr 0.014 0.012 [141]
Q-graphene 0.0186 0.0177 [140]
q-graphenem-graphene – – 0.001580.0011 [138]

Pt/LSG: Pt nanoparticles decorated laser-scribed graphene; LSG: laser-scribed graphene; BPPG: basal plane pyrolytic graphite; EPPG: edge plane pyrolytic graphite; L-
graphene: laser-induced graphene from GO; CVD-Gr: graphene grown on copper foil by chemical vapor deposition; Q-graphene: polyhedral structure graphene; q-graphene:
few-layer (termed quasi-) graphene grown via CVD; m-graphene: mono-layer graphene grown via CVD.

LSG with numerous edge plane sites and plenty of available elec- and the restacking of layers, which leads to decreased surface area
trochemical active surface area. due to the inherent nature of graphene and consequently influ-
ences the detection limit of bioanalytes. The 3D LSG scaffold may
Electrochemical biosensing be a better choice to circumvent the above issues. Anchoring 1-
pyrenebutyric acid to LSG followed by the covalent attachment of
An important aspect of using the graphene-based platform an aptamer in LSG-based biosensor displayed extremely low detec-
in electrochemical bio-sensing is its effective immobilization of tion limits of thrombin at a concentration of 1 pM in the buffer and
bio-enzymes [142]. Many of the sensing platforms, including the 5 pM in the complex matrix of serum (Fig. 10a, b) [143].
commercialized glucometers, are based on enzymatic reactions Araujo et al. demonstrated laser scribing fabrication of electro-
with bio-analytes. In this regard, graphene offers a 2D conductive chemical paper-based analytical devices by pyrolyzing the surface
plane with the high surface area to hold enzymes and simul- of paperboard as shown in Fig. 10c [144]. This is a single step
taneously provide conducting paths for the electrons generated fabrication of non-graphitizing carbon material with aluminosili-
during the biochemical reactions. However, the critical issues in cate nanoparticles and this composite material was employed in
real graphene device fabrication are the requirement of the binder detecting ascorbic acid and caffeic acid (important antioxidants
94 N. Kurra et al. / Nano Today 24 (2019) 81–102

Fig. 11. (a) Nonenzymatic glucose sensor fabrication by electrodeposition of Cu nanoparticles on LSG platform (inset), interference test of the LSG/Cu-NPs sensor in 0.1 M
NaOH solution containing the 1 mM of glucose and the 0.1 mM of interfering species. Adapted with permission from reference [145]. Copyright 2017, Elsevier. (b) Detection
of biogenic enzymes from food samples by Cu sensitized LSG sensors towards food safety, normalized peak area used to calculate total BA content from the 3 successive
injections of supernatant from non-fermented and fermented fish paste. Adapted with permission from reference [148]. Copyright 2018, MDPI.

present in food). These prototype electrochemical sensors were testing fish paste before and after solid-state fermentation with
used for electrochemical sensing of picric acid using differential lactic acid bacteria (Fig. 11b). This was analyzed by normalizing
pulse voltammetry with improved sensitivity in the concentration the peak area for the fermented and fresh samples and calculated
range of 0.48–2.0 mM (Fig. 10d). Such kind of cost-effective fabrica- BA levels in the fermented sample were 19.24 ± 8.21 histamine/kg
tion of paper-based analytical devices may be suitable for a variety fish paste. Low-cost and rapid fabrication of LSG biosensors can be
of applications including clinical and forensic fields. useful for biogenic amine estimation from a variety of food samples,
may serve as an indicator for food safety and quality.
Nonenzymatic glucose detection
pH sensors
Implantable glucose biosensors are emerging as they can offer
continuous monitoring of blood glucose of diabetic patients. LDG Rahimi et al. demonstrated the fabrication of a highly
may be a right choice of platform as it offers high electronic conduc- stretchable electrochemical pH sensor based on conductive
tivity beside having a high electrochemically active surface area. polyaniline/LIG composite (see Fig. 12a-f). The CO2 laser was
Lin et al., developed nonenzymatic glucose sensor based on LSG employed to pyrolyze PI sheet to fabricate graphitic interconnects
platform [145]. Catalytic behavior of electrodeposited Cu nanopar- followed by machining of PI sheet. The porous conductive graphitic
ticles was exploited towards glucose oxidation while exhibiting carbon was modified by polyaniline as a pH-sensitive electrode.
linear detection range from 1 ␮M to 4.54 mM at a high sensi- Polyaniline played multiple roles as the conductive filler, binding
tivity of 1.518 mA mM−1 cm-2 and low limit of detection of 0.35 material, and pH-sensitive membrane. As shown in Fig. 12 g, the pH
␮M. Further, they demonstrated the selective detection of glu- sensor was tested through the unit change in the pH value (from
cose in the presence of other interfering species in the blood 4 to 10) and it exhibited distinct potential change at each pH level
including dopamine, uric acid, sucrose, fructose, and lactose. The with an average response time of 58 s. The pH sensor displayed
anti-interference property of the developed glucose sensor was a linear sensitivity of −53 mV/pH with a correlation coefficient of
certified by successive injection of 1 mM of glucose and 100 ␮M r2 = 0.976 (Fig. 12h). The excellent stability under 100% longitudinal
of interfering species (Fig. 11a). Negligible current response from strain in different pH solutions may be useful in developing future
the other species in contrast to glucose current response makes the wearable point-of-care applications [149].
developed sensor highly selective to the glucose detection. LIG patterns were employed as sensors for monitoring the
Similarly, Bavarian et al. demonstrated a novel and highly sen- quality of water through the detection of unwanted pollutants.
sitive disposable non-enzymatic glucose sensor strip using a direct For instance, Alahi et al., measured the concentration of nitrate-
laser engraved graphene (DLEG) decorated with copper nanocubes N present in the water using graphene sensors [150]. They used
[146]. The prototype glucose sensor displayed excellent selectiv- electrochemical impedance spectroscopy (EIS) to characterize the
ity, sensitivity (4,532.2 ␮A/mM.cm2 ), low detection limit (250 nM), developed graphene sensors to monitor the quality of water in real
high reproducibility (96.8%), stability (97.4%) and a suitable linear time (1–70 ppm) and test the salinity. Cheng et al. demonstrated
range of 25 ␮M - 4 mM. Zhang et al. reported a new approach for the LIG based sensors for atto- to femtomolar level detection of bisphe-
scalable construction of LIG patterns on diverse substrates by using nol A (BPA) [151]. They immobilized BPA-specific aptamer onto
phenolic resin (PR) as the precursor [147]. The fabricated electro- LIG surface as the probe, and its binding with BPA at the electrode
chemical glucose biosensors exhibited a good linear relationship was detected by capacitive sensing. Like other methods, such as
between the concentrations of glucose ranging from 0.2 to 10 mM. capacitive sensing methods for detecting Bisphenol A, salinity test-
LSG biosensors were also employed for the detection of biogenic ing explores the multi-dimensional sensing asset of LIG platforms
amines, which are produced as a result of microbial metabolism of [151,152].
food products. Reagent-free food safety biosensor was fabricated by
functionalizing graphene platform with copper microparticles and Electrocatalysis
diamine oxidase [148]. Such kind of biosensors showed an average
histamine sensitivity of 23.3 ␮A/mM, a lower detection limit of 11.6 Due to the limited availability of fossil fuels and adverse environ-
␮M, and a response time of 7.3 s. Further, the selectivity of LSG mental issues regarding consumption, many efforts have recently
biosensor towards the level of BA concentration was analyzed by been made on critical renewable energy technologies such as
 N. Kurra et al. / Nano Today 24 (2019) 81–102 95

Fig. 12. Fabrication of stretchable pH sensors. (a) Bonding of polyimide to the Ecoflex through silane treatment. (b) serpentine carbon patterns by laser irradiation, (c) spray
coated polyaniline onto porous conductive carbon. (d) Machining of polyimide sheet. (e) Removal of excess of polyaniline. (f) Encapsulation of interconnects by another
Ecoflex layer followed by the deposition of Ag/AgCl and solid electrolyte. (g) Dynamic pH response of the pH sensor to the unit decrease and increase of pH. (h) Potentiometric
responses of a pH sensor to various longitudinal strains in different pH buffer solutions. Adapted with permission from reference [149]. Copyright 2017, American Chemical
Society.

fuel cells, batteries, and electrochemical water splitting. The basic Oxygen reduction/evolution reaction catalysts
reactions for these energy alternatives include oxygen reduction
reaction (ORR), oxygen evolution reaction (OER) and hydrogen evo- LDG can meet these requirements as a 3D scaffold for loading
lution reaction (HER) catalysts in addition to offering mechanical and conductive support.
Ye et al. employed direct laser scribing of metal complex-containing
ORR : 2H+ +1/2O2 +2e− → H2 O (1) polyimide for in-situ formation of metal oxide nanocrystals into
graphitic architecture [160]. They illustrated the generality of this
OER : H2 O → 1/2O2 +2H+ +2e− (2)
approach by employing Co-, Mo- and Fe-based metal complexes
HER : 2H+ +2e− → H2 (3) that subsequently transformed into metal oxides with the simul-
taneous transformation of polyimide into the graphitic scaffold
These reactions require efficient catalysts to accelerate reaction (Fig. 13a). Furthermore, they demonstrated the ORR electrocat-
kinetics for the feasible electrolyzer. To this end, noble metals, tran- alytic activity of various metal oxides-LIG and analyzed using Tafel
sition metal chalcogenides, carbides, phosphides, and oxides have slopes (Fig. 13b). Among the three types of composites, 5Fe-LIG-
been studied as efficient electrocatalysts for both HER and ORR A has a Tafel slope of 102 mV/decade, which revealed lower ORR
[153–156]. However, the use of these catalysts as sole electrodes activity compared to 5Co-LIG-A and 5Mo-LIG-A. This study demon-
invites many issues, such as particle agglomeration and prohibitive strated that controlled doping and tunable metal oxide structures
cost (for noble metals) and the moderate electronic conductivity bonded to LIG as a direct strategy for designing advanced and effi-
of transition metal dichalcogenides (TMDs) [157,158]. Developing cient electrocatalysts.
technology that will markedly minimize noble metal usage while Zhang et al. demonstrated that oxidized LIG is an efficient elec-
preventing agglomeration with increased electronic conductivity trocatalyst for OER and ORR [161]. The oxygen plasma-treated
and effective utilization of the catalyst is critical for the future LIG surface exhibited increased activity in the oxygen reduction
‘hydrogen economy’. One strategy could be the direct employment reaction. This was attributed to the enhanced adsorption of OER
of a minimal amount of the catalyst on a self-supported high surface intermediates. It was further suggested that LIG-O could be a
area conductive carbon with effective utilization [159]. promising metal-free catalyst for water splitting and metal-air/O2
96 N. Kurra et al. / Nano Today 24 (2019) 81–102

Fig. 13. (a) Formation of Mo-LIG by laser induction on MC-PI film. (b) Tafel plots of 5Co-LIG-A, 5Mo-LIG-A, and 5Fe-LIG-A, derived by mass-transport correction of corre-
sponding RDE data. Adapted with permission from reference [160]. Copyright 2015, American Chemical Society. The LSV profiles of the LIG-Co-P for (c) HER and d) OER in
comparison with bare LIG. Corresponding Tafel plots are shown in the insets. Adapted with permission from reference [162]. Copyright 2017, American Chemical Society.

Table 4 HER catalysts

Comparison of HER, OER and ORR performance of various LDG-based electrodes.

HER electrode Onset potential (V) Tafel slope References Pranati et al. demonstrated the efficient use of Pt electrocat-
material at J = −10 mA/cm2 (mV/dec) alysts by atomic layer deposition over LSG for HER. Since LSG is
Pt/LSG200 (HER) −0.131 72 [70] porous and conductive, atomic layer deposition (ALD) offered a
Laser-induced −0.216 64 [157] conformal deposition of Pt catalysts that exhibited excellent HER
MoS2 /carbon performance. The HER performance was optimized with respect to
hybrids (HER)
loading Pt through a number of ALD cycles. It was observed that the
Pt-LIG (HER) −0.109 83
Co-P-LIG (HER) −0.141 54 onset potential drops drastically at about 200 ALD cycles, at which
[162]
Co-P-LIG (OER) +0.364 84 point the cathodic current density rose rapidly and approached
NiFe-LIG (OER) +0.292 49 that of commercial Pt/C. This strategy provides an avenue for min-
5Co-LIG-A (ORR) – 50
imal yet effective usage of Pt, leading to enhanced HER activity
5Mo-LIG-A (ORR) – 57 [160]
5Fe-LIG-(ORR) – 102 (Fig. 14a,b) [70]. Similarly, LIG showed promise in synthesizing
MoS2 /carbon composite structure in a single-step laser irradiation
(Fig. 14c) [163]. The precursor solution composed of citric acid-Mo-
S precursors led to the in-situ synthesis of MoS2 nanoparticles after
laser irradiation. The Tafel slope of bulk MoS2 was compared with
batteries. Pre-doped Pt-complex into PI was transformed into LIG- hydrothermal and laser-scribed MoS2 /carbon hybrids (Fig. 14 d).
Pt under laser irradiation in the H2 /Ar atmosphere. Similarly, after The higher HER activity of the laser-scribed MoS2 /carbon hybrid
the formation of LIG, catalysts such as NiFe and Co-P layers were over other MoS2 samples can be attributed to the intimate contact
electrodeposited on conductive LIG [162]. LIG-Co-P exhibits bifunc- of MoS2 nanoparticles to the conductive carbon matrix and MoS2
tional catalytic activity, causing both HER and OER activities in an NPs with enhanced catalytic sites. Therefore, the laser scribing tech-
alkaline medium (Fig. 13 c,d). As expected, LIG displayed no cat- nique offers the fabrication of desired catalysts or hybrids through
alytic activity, which is evident from the LSV profiles (the black pre-designing the precursor solution. This could lead to fabricating
curves in Fig. 13c and d). Catalytic LIG scaffolds thus offer a prac- micro fuel cells and microcatalytic reactors.
tical solution for electrochemical water splitting and can likely be
used to construct devices for CO2 reduction and ORR. Furthermore, Other exotic applications
the integration of LIG electrodes produces a full device for splitting
water into H2 and O2 . Table 4 displays a comparison of HER, OER In the fabrication of on-chip micro-supercapacitors and electro-
and ORR performance of various LDG-based electrodes. This is the chemical storage of Na-ions, LDG offers advantages such as tunable
reported literature on using LDG as a support for various catalysts morphology, functionality, controllable doping, and composite for-
in water splitting to date. Given the versatile nature of graphitic mation. LDG also supports the binding of a variety of catalytic
electrodes, more efforts are necessary to design competent catalyst particles to develop LDG-based catalysts. The following are some
electrodes for HER, ORR and OER towards creating future energy exotic applications of LDG electrodes in the fields of bio-medical
resources [70,153,160,162]. and electronics.
 N. Kurra et al. / Nano Today 24 (2019) 81–102 97

Fig. 14. (a) Digital photograph illustrating a 3-electrode setup comprising of a LSG-based electrode as a working, Pt wire counter and Ag/AgCl as reference electrodes in
0.5 M H2 SO4 electrolyte. The inset illustrates the instantaneous evolution of H2 bubbles upon the start of the LSV cycle. (b) LSV displaying HER onset region for LSG and
Pt/LSG electrodes compared to commercial Pt/C. Adapted with permission from reference [70]. Copyright 2017, Royal Society of Chemistry. (c) Scheme of the DLW method
in fabricating arbitrary patterns composed of MoS2 /carbon hybrids. (d) Tafel plots of Pt/C, bulk MoS2 , hydrothermal MoS2, and laser-induced MoS2 /carbon hybrids. Adapted
with permission from reference [161]. Copyright 2016, Royal Society of Chemistry.

Fig. 15. Sulfur-doped graphene formation on polysulfone membranes through laser induction. Antifouling and antimicrobial properties of sulfur-doped LIG-based PSU
membranes. Adapted with permission from reference [71]. Copyright 2018, American Chemical Society.

Antifouling properties layer of polysulfone membranes into LIG through laser irradiation
(Fig. 15) [71]. S-doped LIG displayed exceptional biofilm resis-
Studies have investigated the antibacterial properties of tance and potent antimicrobial killing effects when treated with
graphene-based nanomaterials, which stem from its nanosized Pseudomonas aeruginosa and mixed bacterial culture. The hybrid
sharp edges and atomic composition. In this context, LIG offers a PES-LIG membrane-electrode ensured complete elimination of
scaffold rich in edge plane sites and functionalities. A recent study bacterial viability in the permeate (6-log reduction) in a flow-
by Singh et al. demonstrated the antimicrobial and anti-biofilm through filtration mode at a water flux of ∼500 L m−2 h−1 (2.5 V)
properties of LIG based on physical and electrical contact of the and at ∼22 000 L m−2 h−1 (20 V). The functional PSU-LIG, PES-LIG
bacterial cells to the LIG surfaces [71]. This opened new avenues and PPSU-LIG surfaces have the potential to be incorporated into
for exploring LIG as a biofouling platform. bio-medical and environmental devices and technologies. This kind
Another study by the same group revealed the active micro- of anti-biofilm activity of LIG surfaces and electrodes may be an effi-
bial killing function of sulfur-doped LIG by transforming the top cient way to protect surfaces that are susceptible to biofouling in
98 N. Kurra et al. / Nano Today 24 (2019) 81–102

Fig. 16. (a) Graphene earphone in a commercial earphone casing. (b) Training the dog through the earphone. The dog stands up after receiving a familiar 35 kHz signal. (c)
One step laser induction of PI to make laser-derived graphene using the blue laser. (d) The artificial throat can detect the movement of the throat and generate controllable
sound. Adapted with permission from reference [81]. Copyright 2014, American Chemical Society. (e) Top panel: changes in resistance values with respect to a cough,
hum, screaming etc. Bottom panel: High-volume, low-volume and elongated tone hum are detected by the LIG intelligent throat and converted into high-volume 10 kHz,
low-volume 10 kHz and low-volume 5 kHz sound, respectively. Adapted with permission from reference [72]. Copyright 2017, Nature Publishing Group.

environmental applications, specifically in water treatment tech- tude of resistance values (Fig. 16e). These results indicate that a LIG
nology. Lu et al. recently employed 3D graphene electrodes for cell artificial throat can convert unknown sounds into controllable and
alignment and tissue engineering, opening new avenues for flexi- predesigned sounds. A LIG-based artificial throat may be useful for
ble graphene patterns for 3D cell or tissue culture to promote tissue voice control devices for disabled people.
engineering and drug testing applications [164]. Luo et al. employed LIG patterns on PI as flexible piezore-
sistive sensors in probing gesture registration and man-machine
interactions [58]. The graphitic sensor gauge factor displayed an
Electroacoustic applications
exponential dependence on the ratio of the laser power to the
scanning speed, which is key in controlling the sensitivity of the
LDG can also be suitable for certain electronic applications,
graphitic piezoresistive sensor. The optimized device exhibited a
although it is not as high quality as the graphene obtained through
high gauge factor of 1̃12. The versatile graphitic sensor can detect
mechanical exfoliation and high-temperature growth methods.
finger gestures and heartbeats, indicating that the sensor is sen-
Tian et al. demonstrated the wafer-scale fabrication of graphene
sitive to feeble mechanical motions. Tian et al. also reported a
earphone units through the laser scribing approach (Fig. 16a) [81].
GO-derived LSG-based strain sensor that offered a good linear
During the laser scribing process, the rapid expansion of graphene
response to strain and excellent multi-cycle operation [165]. Strong
layers resulted in air gaps between layers that can prevent thermal
et al. demonstrated the use of interdigitated LSG electrodes as
leakage to the substrate. It was revealed that after being tested over
a sensing platform for NO2 gas. The LSG-based sensor displayed
a sound frequency ranging from 100 Hz to 50 kHz, the graphene
reversible operation while detecting up to 20 ppm of NO2 gas in
earphone exhibited a reasonably flat frequency response (Fig. 16
the dry air [69].
b). The LSG-based earphone was useful not only for human beings
The highly conductive, porous and flexible nature of LIG and,
(whose sound frequency range is 20 Hz - 20 kHz) but also for com-
more importantly, its potential to be patterned into any desired
munication with dogs through 35 kHz sound waves.
design has attracted a diverse community. For instance, Lin et al.
Tao et al. demonstrated the fabrication of an artificial throat
reported the lithography-free monolithic fabrication of a flexible
based on LIG on a polyimide substrate [72]. The key characteristics
ZnS/SnO2 ultraviolet photodetector device, in which in-situ LIG-
of LIG include high thermal conductivity with low heat capac-
like materials served as lateral electrodes [166]. Such a device is
ity and porous morphology. The former is needed to serve as a
expected to have high mechanical flexibility and excellent opto-
thermoacoustic sound source; the latter can detect weak vibra-
electronic performance due to robust interfaces between LIG and
tions and is suitable for sound detection. Therefore, LIG offers the
ZnS/SnO2 . Graphene achieved a remarkable thermal conductiv-
single-step fabrication of a smart acoustic device that not only gen-
ity enhancement from 0.7 to greater than 1.7 W/m-K by adding
erates but also detects sound [72]. The fabrication of an artificial
polymer, suggesting that this process could be useful for com-
throat is very simple. A rectangular LIG was produced on a PI sheet
mercial thermal interfacial applications. A comparison of the
after irradiating it with a 450 nm laser (Fig. 16c). This kind of LIG
performance of LDG devices versus graphene produced by other
pattern integrates the functions of emitting and detecting sounds
means for a variety of applications is summarized in Table 5
as illustrated in Fig. 16d. To test the LIG, it was attached to the
[51,52,58,65,73,83,104,105,118,146,147,165,167–179].
human throat and simple throat vibrations, including a cough, hum,
scream, swallow and nod, were detected by recording the magni-
 N. Kurra et al. / Nano Today 24 (2019) 81–102 99

Table 5
Comparison of the performance of LDG versus graphene electrodes produced by other means for a variety of applications.

Devices Device type and performance metrics References

Microsupercapacitor Type Specific capacitance (mF/cm2 ) Power density (W/cm3 ) Energy density (mWh/cm3 )

LDG (4 ␮m) 4 100 1 [52]

BLIG 12.4 3 0.56 [118]
LSG from GO 2.32 200 0.6 [65]
Graphene * 0.7 0.1 1 [167]
Activated carbon 11.6 40 10 [104]
Onion-like carbon (7 ␮m) 1.7 1000 2 [104]
Reduced GO (22 ␮m) 0.51 1.7 0.43 [51]
CNT arrays (80 ␮m) 0.428 0.28 mW/cm2 – [168]
Graphene/CNTs (20 ␮m) 3.93 135 2.42 [169]
Mesocarbon microbead (100 ␮m) 100 0.575 mW/cm2 10 ␮Wh/cm2 [170]
Carbide-derived carbon (50 ␮m) 300 – – [105]

Biosensors Type Sensitivity (␮A/mMcm2 ) Detection potential (mV) Linearity (␮M) Detection limit (␮M)

Dopamine Pt/LSG 6995.6 – 0.5-56 0.07 [73]

LSG 2259.9 – 0.5-32.5 0.27 [73]
3D graphene ⊥ 619.6 0.177 Up to 25 0.025 [171]

Glucose Cu NCs/DLEG 4,532.20 0.55 25-4000 0.25 [146]

LIG␩ – – 0.2-10000 – [147]
LSG/Cu-NPs 1518 0.6 1-4540 0.35 [172]
CuO/GO/GC 262.52 0.7 2.79-2030 0.69 [173]
Cu–N-G 48.13 0.5 4-4500 1.3 [174]
CuOG/GCE 1065 0.6 1-8000 1 [174]

Other sensors Type Patterning method Gauge factor

Strain Total LSG laser scribe with water lift-off ; 673 [175]
LSG with pattern laser scribe 457 [83]
DLW graphitic lines Laser scribe on polyimide 112 [58]
GO derived LSG Laser scribe on GO film 0.11 [165]
GO derived graphene micro-ribbons Laser scribe on GO film 9.49 [165]
nanographene by CVD UV-lithography and reactive ion etching 546 [176]
monolayer graphene by CVD lithography and plasma etching 151 [177]
electrochemical exfoliated graphene flakes stencil printing 1037 [178]
reduced graphene oxide vinyl mask 261.2 [179]

BLIG: Boron-Doped Laser-Induced Graphene.

*
Inkjet printed graphene micro supercapacitor devices with electrochemically exfoliated graphene.
†
RGO prepared by laser reduction and patterning of hydrated graphite oxide films.
⊥3D graphene: Free standing 3D graphene foam.
Cu NCs/DLEG: direct laser engraved graphene (DLEG) decorated with pulse deposited copper nanocubes (CuNCs).
LSG/Cu-NPs: electrodeposited copper nanoparticles on DVD-laser scribed graphene substrate; LIG␩ : laser-induced graphene (LIG) patterns on diverse substrates by using
phenolic resin (PR) as the precursor.
Cu–N-G: Copper nanoparticles (NPs) decorated nitrogen-doped graphene (Cu–N-G).
CuO/graphene (CuOG)-modified glassy carbon (GC) electrode.
DLW graphitic lines: Direct laser write generated graphitic lines; graphene strain sensor (10 mm 10 mm square) graphene micro-ribbons (20 mm width, 0.6 mm long).

Outlook and perspectives ing fine-focused laser beams to allow high-resolution electrode
patterns. In addition, there is a chance to make a large variety
Processing graphene-based materials by conventional ink-jet, of electrodes, including composites of 2D materials, and het-
screen printing, and roll coating techniques often involve the erostructures of LDG materials. These have not been sufficiently
use of solvents and additional binders. Though these techniques explored yet. Embedded electronics and energy storage devices
offer reliable patterning of graphene materials, the performance is may be developed through defocused laser beams. In this case, the
often limited due to agglomeration of graphene layers. Laser-based desired graphitic patterning can be done inside the thickness of
technologies proved to be innovative and scalable approaches the substrate. Since it is possible to control the degree of graphi-
for direct-write (maskless) fabrication of 3D graphene electrodes tization, vertical multi-layer structures can be fabricated through
for on-chip functional devices. Fabricated electrode patterns are graded laser parameters. Such modular multi-layer graphene can
monolithic, binder-free, porous and easy to print. Furthermore, het- exhibit interesting properties when compared to uniform graphene
eroatom doping can be done by controlling the composition of the stacked structure. More detailed doping studies should be carried
precursor film and by lasing in specific gas environments. With the out to modify the physicochemical properties of graphene-based
right selection of precursor material, patterns of multi layer elec- electrodes. Fabrication of vertical graphene architectures should
trode stacks, graphene-metal, and graphene-inorganic composites be studied to increase the LDG density in a given footprint area for
can also be fabricated through direct-write laser lithography. Irre- improved areal performance metrics. Limited research was per-
spective of the initial precursor composition, it is possible to pattern formed using LDG as anodes for mobile-ion batteries, including Al,
graphene and graphene hybrids precisely and directly in a single Mg, Ca and so forth. Most recent studies have used bench-top laser
step according to specific application requirements. processing, but there must be more effort to scale-up this pro-
Despite its remarkable success so far, many challenges remain cess; for example, scalable manufacturing of graphitic electrodes
before this technology can be brought into the market. For instance, through roll-to-roll approach, as illustrated in Fig. 17 [45]. This
the resolution of laser techniques should be improved by employ- technology is viable for the commercialization of on-chip graphitic
100 N. Kurra et al. / Nano Today 24 (2019) 81–102

Fig. 17. Schematic illustration for roll-to-roll (R2R) manufacturing of graphitic electrodes on the PI sheet. Further, the hybrid material can be deposited using a catalyst bath
(optional). Adapted with permission from reference [45]. Copyright 2018, American Chemical Society.

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