Graphene oxide: new opportunities for optoelectronic, electronic

and photonic chips

David J. Moss

Optical Sciences Centre, Swinburne University of Technology, Hawthorn, VIC 3122,

Australia.
Email: [email protected]

Abstract

As a derivative of graphene, graphene oxide (GO) was initially developed by chemists to

emulate some of the key properties of graphene, but it was soon recognized as a unique
material in its own right, addressing an application space that is not accessible to chemical
vapor deposition based materials. Over the past decade, GO has emerged as a new frontier
material with tremendous advances in its material fabrication and quality control over its
properties. These in turn have led to rapid progress in GO based photonics, electronics, and
optoelectronics concepts and devices, evoking new science and paving the way for many
technological breakthroughs with exceptional performance. Here, we review the unique
fundamental characteristics of GO, its thin film fabrication methods, patterning techniques,
and mechanisms for tuning its material properties. This latter capability in particular has
enabled novel advanced functional photonic, electronic, and optoelectronic devices.
Understanding these insights is essential for designing and tailoring GO properties for state-
of-the-art applications including solar energy harvesting, energy storage, medical diagnosis,
image displays, and optical communications. We conclude by discussing the open challenges
and exciting opportunities of this field, together with future prospects for major technological
advancements and breakthroughs.
Keywords: Graphene oxide, 2D materials, integrated optics, nonlinear optics, photonic
integrated circuits
Introduction

Historically, the development of carbon materials has driven, and been accompanied by,
many technological advances. Since the first discovery of buckminsterfullerene (so-called
“bucky-balls”) in 19851, followed by carbon nanotubes (CNTs) in 19912, low-dimensional
forms of carbon materials have attracted tremendous interest. This trend intensified after the
first experimental isolation of two-dimensional (2D) carbon monolayers – graphene – in
20043, and has expanded into many other forms of 2D carbon-based materials that contain
more than just simple carbon atoms.
Graphene oxide (GO), as the most common derivative of graphene, consists of layered
carbon networks decorated with oxygen-containing functional groups (OFGs). The history of
GO dates back to 18594, and its investigation has experienced remarkable advancement in the
past two decades (BOX 1, panel a), in tandem with a surge in interest in graphene-based
materials in general. In the early days of graphene research, GO was a common route to
making imperfect graphene5. Subsequently, the ability of GO to be dispersed in solution
together with the interesting properties that arose when it was stacked into a lamellar structure,
garnered significant attention in its own right. GO provides a flexible material platform for the
attachment of a range of functional organic groups to the surface of a graphene-like carbon
network, yielding functionalized graphene-based materials with a range of unique properties.
In addition, facile solution-based synthesis processes have been developed for GO and its
derivatives, which are attractive for the large-scale manufacturing of carbon-based materials
and devices. Further, GO and its derivatives can be processed into diverse forms such as
suspensions in solution, monolayer nanosheets, free-standing papers, thin membranes, and
fillers in organic or inorganic nanocomposites (BOX 1, panels b ‒ f). All of these have
distinct morphological features that render them highly versatile for many high-tech
applications.
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BOX 1 │History and morphology of GO
The earliest known synthesis of GO was achieved by Oxford chemist B. Brodie, dating back to 18594 ‒
over a century before the discovery of modern carbon materials such as fullerene and CNTs at the end of
20th century, followed by the rise of 2D materials such as graphene3, transition metal dichalcogenides
(TMDCs)6, and black phosphorus (BP)7 after 2004 (panel a). Brodie invented the method for oxidation of
crystalline graphite and synthesized GO via exfoliation of graphite oxide. His method yielded many
atomically thin GO sheets, which perhaps were the earliest synthesized 2D materials, although graphene
itself was unknown at that time. In 1958, Hummers et al. made important modifications to the GO
synthesis method, achieving a shorter reaction time, larger sheet sizes, and without the need for hazardous
ClO2 gas8. Nowadays, the Brodie and Hummers methods are still widely used for GO synthesis with only
minor modifications. The ground-breaking discovery of graphene in 2004 revived the interest in GO, and
increasingly, the evidence has shown that GO is in fact more than just a precursor of graphene, but rather
has its own unique material properties that actually outperform graphene in many applications. The
development of nanofabrication and characterization technologies for GO has led to many exciting
advances in both scientific research and industrial uses in the past decade, such as observation of the atomic
structure of GO on the nanoscale9, the direct laser patterning of GO films 10, the synthesis of high-quality
graphene via GO reduction11, and the integration of 2D GO films on chip with precise control12.
The bulk form of GO is graphite oxide, which is a brownish hydrophilic compound composed of layered
GO sheets (panel b13). Unlike graphene, GO is soluble in aqueous and polar solvents, which allows for
solution-based preparation and processing. Panel c shows the aqueous suspension of exfoliated GO
sheets14. Depending on the concentration of GO sheets, the suspension’s color can vary from light yellow
to dark brown. Panel d shows an atomic force microscope (AFM) image of monolayer GO sheets having a
thickness of about 1.2 nm15. By using different GO synthesis methods, the lateral size can be varied from
several microns to several tens of microns. The exfoliated GO sheets can be used as a raw material to
prepare free-standing papers (panel e16), thin membranes (panel f17), or composite materials18 for different
applications.

GO has a broad range of uses in many core industries that underpin our daily life. In the
past decade, paralleling the growth of photonics, electronics, and their intersection ‒
optoelectronics, GO devices have blossomed, spurred on by GO’s material properties as well
as the advancement of nanofabrication technologies. These devices have underpinned a wide
range of technologies such as solar energy harvesting, energy storage, medical diagnosis,
image displays, and optical communications. In this Review, we summarize the state-of-the-
art of this field. Since both the electronic and optical properties of GO essentially reflect the
response to electromagnetic waves at different frequencies, photonic and electronic
applications of GO are closely related. While GO has been the subject of previous reviews5,19-
21
, here we focus particularly on its applications to photonics, electronics, and optoelectronics,
highlighting the significant progress and achievements over the past decade.
This review is structured as follows. We begin by comparing graphene, GO, and reduced
GO (rGO), in terms of their atomic structure, optical bandgaps, and other fundamental
properties. We then summarize the approaches for GO synthesis, device fabrication, and
modifying its material properties. Next, we outline the optical, electronic, and optoelectronic
properties of GO and rGO, and review the representative work in key areas. Finally, we
discuss the current challenges and future prospects.

Chemical structure & bandgap

In FIG. 1, we compare the atomic structure, bandgap, and high-resolution transmission
electron microscopy (HRTEM) images of pristine graphene (PG), GO, and totally reduced
GO (trGO). Since trGO has no residual oxygen-containing functional groups (OFGs), we
examine it here in order to highlight the contrast between GO and reduced GO (rGO),
together with PG compared with trGO.
As a derivative of PG, GO has different OFGs such as hydroxyl, carboxyl, and carbonyl
groups (FIG. 1a) located either on the carbon basal plane or at the sheet edges. Compared
with PG that consists of only sp2-hybridized carbon atoms, some of the carbon atoms in GO
are sp3 hybridized through σ-bonding with the OFGs, leading to a heterogeneous structure.
Depending on the different synthesis methods and preparation processes, there is a wide
variability in the concentrations of sp2 and sp3 hybridizations, and this can also be affected by
a reduction in OFGs or doping treatments. Together, these all enable a high degree of
flexibility in changing GO’s material properties.
Note that trGO has a defective carbon network that results from the complete reduction of
GO that removes all the OFGs, and so its material properties are close to PG. The high yield
of GO monolayers resulting from solution-based exfoliation provides an attractive method of
mass-producing graphene-like materials. The difference in properties between trGO and PG
mainly results from defects in the trGO. In the past decade, significant progress has been
made towards obtaining high-quality graphene through the reduction of GO, led by methods
based on wet chemistry22 and microwave reduction11.
Fig. 1. Comparison of pristine graphene (PG), graphene oxide (GO), and totally reduced GO (trGO).
a| Schematics of atomic structures. b| Schematics of bandgaps. c| High-resolution transmission
electron microscopy (HRTEM) images. Scale bar for left and middle: 2 nm. Scale bar for right: 1 nm.
Panel c left and middle adapted with permission from REF.9, Wiley-VCH; panel c right adapted with
permission from REF.11, AAAS.

In contrast to PG that has a gapless Dirac cone, GO features an opened bandgap (FIG. 1b),
arising from the isolated sp2 clusters within the sp3 C–O matrix, where the size of the sp2
clusters determines its bandgap. Unreduced GO has a typical bandgap of 2 eV ‒ 3.5 eV,
which can be tuned by varying the sp2 and sp3 concentrations. This has been modeled by first
principles theory23 coupled with experimental characterization17. The reduction of GO can
lead to an increase in the fraction of sp2 bonds, thus reducing the bandgap. The ability to vary
the bandgap of GO enables the tuning of its material properties including the refractive index,
optical absorption, and electrical conductivity, all of which are key for photonic and
electronic applications.
Due to the existence of OFGs, a monolayer GO film has a typical thickness of ~1 nm, which
is much thicker than a monolayer of PG (~0.35 nm). Unlike PG that contains only a sp2
carbon network with a highly uniform surface (FIG. 1c, left panel), GO has a hybrid carbon
network that exhibits a highly disordered structure (FIG. 1c, middle panel). It contains many
different regions including sp2 regions having a preserved honeycomb structure, sp3 regions
with bonded OFGs, and defect regions, which all contribute to a relatively rough surface.
Forming trGO through accurately controlled microwave reduction (FIG. 1c, right panel)
results a highly ordered structure, almost the same as PG, reflecting thorough removal of the
OFGs and nearly perfect reconstruction of the sp2 carbon lattice after the reduction process.

Material synthesis & device fabrication

GO film synthesis
GO nanosheets can be produced on a large-scale by the chemical oxidization of graphite24,
where the hydrophobic graphene surface is converted to hydrophilic GO due to the
attachment of OFGs. The hydrophilic property of GO allows for the dissolving of GO flakes
in water, which enables various solution-based film fabrication methods as shown in FIG. 2.
More importantly, it then becomes feasible to further modify the intrinsic material properties
of GO by controlling the content of OFGs through various reduction methods 25. These unique
features make GO an excellent material platform for multifunctional devices.
A number of film synthesis methods have been demonstrated, which can be categorized
according to their degree of control over the film thickness. We first review solution dropping
methods that have coarse thickness control, such as drop casting (FIG. 2a), spray coating
(FIG. 2b), and spin coating (FIG. 2c). Drop casting is the simplest method of fabricating GO
films, where drops of GO solution are directly applied on a substrate and form a film after
drying. The film thickness mainly depends on the concentration and volume of the GO
solution, which are difficult to accurately control, and so result in a low uniformity. In
contrast, smaller drop sizes can be realized by using a spray nozzle, with or without
ultrasonification (FIG. 2b). The tiny droplets that result from this can significantly improve
the uniformity and degree of control over the thickness by controlling the spray time.
Alternatively, the thickness control and uniformity can also be improved by placing the
substrate on a spinning disc and using a spin coating method (FIG. 2c), where the thickness
can controlled by varying the GO solution concentration and spin speed. However, neither of
these methods can create either continuous monolayers or freestanding films, due to their
inability to accurately control the film thickness, together with the poor mechanical strength
of the resulting GO films because of the random orientation of the GO flakes.
By comparison, the film uniformity and thickness can both be controlled better via
filtration methods with controlled pressure (FIG. 2d). By varying the volume of GO flakes
and controlling the GO solution concentration, it is possible to produce highly uniform GO
films with controllable thicknesses. Since the GO films prepared in this way are formed on
porous filter substrates, they typically need to be peeled off from the filter in order to transfer
them to other substrates. It is also possible to obtain freestanding GO films for thick (> 200
nm) films to avoid any undesired influences of the substrate, such as for infrared
applications26. On the other hand, filtration methods are limited in the size of the film areas
they can produce. Further, they are relatively slow in the time needed to dry out the film,
which inceases with film thickness. The Dr Blade method (FIG. 2e) can also be used to
achieve a high degree of control over the thickness and uniformity of the GO film by
controlling the gap between the blade and the substrate27. This method can produce large-area
GO films, and is even amenable to roll-to-roll production methods. However, neither filtration
nor the Dr Blade method are able to control the film accuracy down to the monolayer level.
A low-cost solution-based layer-by-layer GO film fabrication method has recently been
developed17. In this method (FIG. 2f), a monolayer of positively charged polyelectrolyte
polydiallyldimethylammonium chloride (PDDA) is coated on the negatively charged substrate
(such as silica or silicon). Following this, a negatively charged GO monolayer is firmly
attached to the positively charged PDDA layer, enabled by the electrostatic forces caused by
the attachment of OFGs. By iterating the PDDA and GO deposition processes, multiple
GO/PDDA layers can be conformally coated onto arbitrary substrates without the need for
any transfer processes. This method is able to construct GO films with arbitrarily large areas
and shapes. The substrates that have been used with this method include dielectrics (silicon
wafers, glass slides, and cover slips), plastics (curved acrylic lenses and Polyethylene
terephthalate (PET) films), metals (copper and silver), and even substrates composed of
nanostructures (nanoholes in copper and silicon nanopillars)28. In addition, due to the strong
electrostatic force present between the interlayers, the deposited GO films possess outstanding
mechanical strength and excellent flexibility even after extensive bending and twisting tests.
This layer-by-layer film deposition technique can yield large-area ultrathin GO films with a
well controlled film thickness on a nanometer scale. This, together with the ability of
conformal coating over diverse nanostructures, represents a significant advantage for large-
scale manufacturable photonic, electronic, and optoelectronic devices.
Fig. 2. Fabrication methods for GO films. a| Drop casting method, inset: transmission optical
microscopy image of drop-casted GO film. b| Spray coating method, inset: scanning electron
microscope (SEM) image of spray coated GO film. c| Spin coating method, inset: SEM image of spin
coated GO film on cover glass. d| Filtration method, inset: photo of filtrated GO transferred on to a
flexible substrate. e| Dr. Blade method, inset: photo of freestanding GO film prepared by using Dr.
Blade method. f| Layer-by-layer self-assembly method. Insets: SEM image of a 5 layer GO film on a
silicon substrate (top) and GO coated on an A4 size flexible PET substrate (bottom). Panel a right
adapted with permission from REF.29, OSA publishing. Panel b right adapted with permission from
REF.30 , IOP publishing. Panel c right adapted with permission from REF.31 , ACS publications. Panel d
right adapted with permission from REF.32, Springer Nature Limited. Panel e inset adapted with
permission from REF.27, ACS publications. Panel f adapted with permission from REF.17, ACS
publications.
GO reduction
In order to convert GO to graphene-like materials, it is necessary to remove the OFGs, and
this can be done through various reduction methods. The four reduction methods that are
widely used include thermal reduction, chemical reduction, microwave reduction, and laser
reduction25.
Thermal reduction (FIG. 3a) is the most common, where the OFGs are removed by heating
the GO films with a hot plate or oven at temperatures between 200 °C and 1000 °C33. At
higher temperatures the carbon network begins to damage. In order to protect the carbon
network from burning at high temperature, the thermal reduction can be performed in nitrogen
(N2), argon (Ar) or vacuum atmospheres. Although thermal reduction can process large
volumes of GO, it cannot completely remove OFGs since C=O bonds are stronger than C=C
bonds in the GO carbon lattice network. The degree of reduction can be increased by using
chemical reduction in solution with reducing agents capable of targeting specific bonds (FIG.
3b). However, while chemical reactions can almost completely remove the OFGs34,35, it is
still necessary to fabricate rGO films after reduction, which is much more challenging than
for GO films because of the hydrophobic properties of the rGO flakes.
More recently, microwave methods have been developed for GO reduction (FIG. 3c), and
these typically consist of a two-step process11. First, the GO film is mildly pre-reduced using
thermal reduction to improve its conductivity. This is followed by a complete reduction of the
pre-reduced GO film in a microwave oven. This method has proven effective for removing
the OFGs and restoring the carbon network, and can yield high quality rGO approaching that
of PG. However, it is best applied to free-standing GO films since the electrical properties of
the substrate can significantly affect the reduction process. Thus, it is not suitable for
applications to semiconductor or metal substrates.
Lastly, laser photo-reduction (FIG. 3d) is currently regarded as one of the most effective
and flexible methods of producing rGO32,36, where the GO films are converted in-situ to rGO
films. This method can be used to achieve film patterning, thus providing a useful approach to
create functional devices37,38 39-41
. In addition, laser treatment can simultaneously reduce and
dope GO42, and does not use harsh or toxic chemicals, nor does it require high temperatures.
During laser reduction, the OFGs are removed and sp2 graphene domains are formed. To
achieve high quality rGO, the OFGs need to be completely removed without destroying the
sp2 domains. Depending on the photon energy of the laser being used, laser photo-reduction
can be classified into either photochemical or photothermal reduction43,44. It has been
demonstrated that the photon energy threshold for photochemical reduction is 3.2 eV (i.e., λ =
390 nm), while a photon energy of < 3.2 eV (i.e., λ > 390 nm) generally yields photothermal
reduction43.

Fig. 3. GO reduction methods. a| Thermal reduction method, inset: SEM image of thermally reduced
GO film and the X-ray photoelectron spectroscopy (XPS) spectrum. b| Chemical reduction method,
inset: SEM image of chemically reduced GO film on cover glass and the XPS spectrum. c| Microwave
reduction method, inset: SEM image of microwave reduced GO film and the XPS spectrum. d| Laser
reduction method, inset: optical microscopy image of laser reduced GO film and the XPS spectrum.
Panel a right adapted with permission from REF.33, MDPI. Panel b right adapted with permission
from REF.34, RSC Publishing and REF.35, MDPI. Panel c right adapted with permission from REF.11,
AAAS. Panel d right adapted with permission from REF.36, OSA Publishing.
In the photothermal process, the light is absorbed by the entire GO structure, which heats
up the GO molecules, increasing the temperature linearly with power. Several stages can be
identified in the reduction process based on their temperature window45. Initially, water in the
GO layers is evaporated, followed by the elimination of the OFGs at 200 °C, beginning with
C-COOH groups due to their lowest binding energy. This is followed by the removal of C-
OH groups at around 600 °C, after which the C-O-C groups are finally removed at 800 °C.
The graphene sp2 C=C network itself begins to break near 1000 °C. Increasing the
temperature further results in the complete burning of the aromatic graphene network. Since
the sp3 C-C bond has a lower binding energy than any of the C-O bonds, breaking them
introduces defects in the graphene network. Hence, photothermal reduction has a limited
reduction ability with regards to C=O species, and it is challenging to achieve nearly complete
reduction using this method alone without suffering from collateral damage to the graphene
network.
In contrast, photochemical reduction can remove OFGs effectively and restore the aromatic
domain in graphene through the non-resonant Stark effect 46. Conventional photochemical
reduction methods use either photocatalysts47 or short wavelength light sources, and each
have their trade-offs. Laser reduction without photocatalysts is advantageous, since the
catalysts may affect the overall properties of the laser reduced GO. On the other hand, not
using catalysts requires a short wavelength laser such as an excimer laser (λ = 248 nm)48 or
even shorter extreme-ultraviolet sources (λ = 46.9 nm)49, where the penetration depth within
the GO film is typically only a few 10’s of nanometres. This makes it challenging to process
very thick films.
In comparison, longer wavelength (visible and near infrared) femtosecond lasers have been
applied to reduce GO films with minimal thermal effects and penetrate deeper into materials,
achieving a relatively high C: O ratio (8:1)50. The high optical intensities involved with
focused femtosecond laser irradiation can lead to multiphoton absorption, thus resulting in
thermal relaxation that induces both photothermal and photochemical processes43.
Multiphoton absorption can also lead to a higher spatial resolution, potentially reaching the
nanometer scale32, which is highly advantageous for fabricating photonic and electronic
devices in a single step. During the femtosecond laser reduction, the material properties of
GO, such as the refractive index, light absorption, conductivity, surface hydrophilicity, are
modified by detaching the OFGs. This has been widely used for tailoring GO’s material
properties in many photonic and electronic devices10,51.

Patterning and nanostructuring

Patterning and nanostructuring of GO or rGO films are generally required during device
fabrication to realize different functionalities12,52,53, and are sometimes achieved in tandem
with GO reduction processes. In FIG. 4, we summarize the methods for GO and rGO
patterning and nanostructuring. Here nanostructuring is distinct from patterning in that it can
be used to fabricate 3D nanostructures in contrast to planar patterns.
It is possible to create 2D patterns with relatively low resolution (in the range of 10’s to
100’s of microns) via the widely used inkjet printing method54,55. During this process (FIG.
4a), the substrate is placed on a hot plate, which helps to quickly dry out the printed ink
droplets. The ink solution can be either GO or rGO solutions, each requiring different
solvents that affect the viscosity and resolution of the inkjet printing process. If a GO solution
is used and the temperature is set to below the reduction threshold (< 80 °C), it is possible to
produce GO patterns. On the other hand, rGO patterns can be achieved by either directly
using rGO solutions or by reducing the GO patterns. Since GO solutions can use water as a
solvent, which has a very low viscosity, it is generally preferable to achieve high resolution
patterns. Inkjet-printed GO/rGO patterns are generally used for sensing or energy storage
applications55,56, which don’t require high spatial resolution. In comparison, as mentioned in
the previously, focused laser beam photoreduction can produce micro/nanopatterns (FIG. 4b)
to fabricate devices such as electrodes57 and supercapacitors58,59. By increasing the laser
power, the laser-reduced GO films can actually be ablated (FIG. 4c) to fabricate grooves or
holes51,60. Patterning such grooves at designed positions can produce ultrathin gratings51 and
metalenses60,61.
The layer-by-layer self-assembly method can produce conformally coated GO films on
substrates that contain nanostructures (FIG. 4d), which is usually challenging for the methods
based on layer transfer or physical vapor deposition. Along with the GO reduction methods,
this allows for the further exploitation of the material properties of GO and rGO by enhancing
the overlap with an optical mode or by taking advantage of resonant enhancement effects in
nanocavities28.
Conventional semiconductor patterning methods such as lithography and lift-off can also
be used, either for selective film removal or for selective film coating over desired areas, as
shown in FIG. 4e for a microring resonator (MRR) with a patterned GO film12. These
methods often involve multiple steps, including coating, patterning, and developing the
photoresist to create the pattern, followed by coating the GO films and finishing off by
removing the photoresist. As compared with laser patterning methods, these approaches
enable more accurate control of the size and position of the film patterns for coating small
areas on a large substrate with either GO or rGO.
Fig. 4. Patterning of GO/rGO film. a| Production of micropatterns by using inject printing. Inset: SEM
image of the inkjet printed electrode pattern. b| Generation of nanostructure by using laser
photoreduction. Inset: AFM image of a graphene metalens. c| Generation of nanostructure by using
laser ablation. Inset: SEM of a graphene nanograting. d| Conformal coating of GO metamaterials on
prefabricated nanostructure. Inset: SEM image of conformally coated nanostructures. e| Patterning
GO film on photonic devices using lithography and lift-off method. Inset: optical microscopy image of
GO film coated on a microring resonator (MRR). f| Generation of porous graphene material via flash
photoreduction. Inset: SEM image of the porous graphene. Panel a right adapted with permission
from REF.54, Wiley-VCH. Panel b right adapted with permission from REF.62, OEJ. Panel c right
adapted with permission from REF.51, Springer Nature Limited. Panel d right adapted with permission
from REF.28, Springer Nature Limited. Panel e right adapted with permission from REF.12, Wiley-VCH.
Panel f right adapted with permission from REF.63, Elsevier Publishing.
Porous graphene nanostructures can be created efficiently and quickly by using a single
flash light pulse63 to reduce GO films (FIG. 4f). Flash lamp based photoreduction is similar,
yet complementary, to laser photoreduction, offering similar advantages but with the added
benefits such as improved efficiency, scalability, and accessibility. The pulsewidths of flash
lamps (typically on the order of milliseconds) tend to be much longer than lasers and with
much broader and incoherent spectral bandwidths. Hence, another advantage is that material
ablation is much less likely than with femtosecond laser reduction, in situations where this is
not desired.
In creating porous graphene nanostructures, the flashlamp pulse heats the GO film up to
2000 °C at an ultrafast rate up to 108 K/min63 , which completely reduces the GO to a
graphene-like material. During this process, gas products, including CO2, CO, and H2O, are
rapidly released and expanded, resulting in the generation of nanopores inside the rGO films
and 3D porous structures with tunable porosity. The porous structures, which can enhance
light absorption by up to 99 %64, are ideal for light trapping. Another advantage of this
process is that the random distribution of pore sizes results in a very broadband absorption
covering the entire solar spectrum. This can result in a near ideal black body absorption
spectrum which is highly useful for applications such as solar energy harvesting65. Combining
the large surface area of the porous structures with the high thermal conductivity of rGO
allows solar water vapour generation66. Furthermore, the high electrical conductivity of these
structures allows for the use of porous rGO as electrodes for electrochemical energy storage
devices27,63,67-69.
The patterning resolution of GO films is important in that it reflects the quality and level of
fabrication, and is determined by both the patterning method and film quality. Inkjet printing
has the lowest resolution on the order of microns. For laser patterning of GO films, the
resolution approaches the diffraction-limit (i.e., 0.5λ / NA, where NA is the numerical
aperture of focusing lens, and λ is the wavelength), which is typically > 200 nm. To achieve a
high resolution, a high NA focusing lens combined with short working wavelengths is needed.
For patterning of self-assembled GO films based on lithography followed by lift-off or
alternatively on conformal coating of pre-patterned nanostructures, the patterning resolution is
mainly limited by the minimum gap size at scales > 300 nm, and by the GO flake size at finer
scales < 150 nm. The GO flake size, typically on the order of 100’s nm, can be reduced
further using modified oxidation and exfoliation methods70, which can reduce the resolution
limit yet further.

Linear optical properties

The diverse range of OFGs present in GO results in a wide variability in its optical
properties in comparison with PG. These properties can be tuned, or engineered, continuously
by varying the degree of reduction, ultimately approaching that of PG. In this section, we
summarize the linear optical properties of GO and rGO and review their relevant applications.
Solar absorption
Like PG, rGO can absorb radiation over a very broad wavelength range from the ultraviolet
to the terahertz regime19,71. The ability to achieve strong light absorbance in the solar spectral
regime (FIG. 5a), along with a high carrier mobility, has enabled rGO to form the basis of
high-performance solar devices. Although commercial silicon-based solar devices are mature,
they are intrinsically limited in their light-energy conversion efficiency due to the poor light
absorption of silicon across the solar spectrum. Another limitation of state-of-the-art solar
devices is their need for special materials such as platinum and indium (e.g., for transparent
indium tin oxide (ITO) electrodes), which are not only rare and expensive but also toxic. In
contrast, rGO is derived from earth-abundant material and has high absorption across the
entire solar spectrum.
A rGO solar absorber51 is shown in FIG. 5b. Gratings with a thickness of 90 nm formed by
rGO were fabricated by combining the layer-by-layer self-assembly method with direct laser
writing (DLW). A high absorptivity of ~85% for unpolarized light across nearly the entire
solar spectrum was achieved. The solar absorber also exhibited other advantages such as
maintaining high light absorption over large incident angles and efficient heating under
natural sunlight. A solar absorber based on a rGO film conformally coated on 3D metallic
resonant structure was also reported28. The resonant structure was used to enhance the
absorption specifically across the solar spectrum. This, together with the high thermal
conductivity of rGO, resulted in a strong solar-selective absorption of omnidirectional light,
yielding a solar-to-thermal conversion efficiency of up to ~90.1%.
Fig. 5. Linear optical properties and applications. a| Solar radiation spectrum and broadband high
material extinction coefficient k of rGO. b| A rGO solar absorber. c| Change of refractive index n and
extinction coefficient k from GO to trGO. d| A GO flat lens with 3D subwavelength focusing (left) and
3D holographic imaging based on photoreduction of GO (right). e| Schematic showing anisotropic
loss of light propagating along a 2D GO film. f| A GO waveguide polarizer. g| Schematic showing
electric-field induced orientation of GO liquid crystal (GO-LC). h| Birefringent textures of between
crossed polarizers (left) and an electro-optic GO-LC switching (right). Panel b adapted with
permission from REF.51, Springer Nature Limited. Panel d left adapted with permission from REF.32,
Springer Nature Limited; panel d right adapted with permission from REF.72, Springer Nature Limited.
Panel f adapted with permission from REF.12, Wiley-VCH. Panel h adapted with permission from
REF.73, Springer Nature Limited.
Tunable refractive index and extinction coefficient
With a typical bandgap > 2 eV, pure unreduced GO displays an optical absorption that
varies from the visible to the infrared wavelengths. In the near-infrared regime, a low material
extinction coefficient k of ~0.005 has been achieved for self-assembled GO films12, which is
over two orders of magnitude lower than PG. In the visible and near ultraviolet regimes, the k
of GO is typically > 0.1, mainly due to the π–π* transitions of C=C. On the other hand, GO
displays a relatively moderate dispersion in its optical refractive index n, which is around 2
from the near-infrared to the mid-infrared regime26. For rGO, both n and k increase and
approach that of PG as the degree of reduction increases (FIG. 5c). In contrast to bulk
materials that usually have limited tuning ranges for n and k, GO has a very large tuning range
for both n (∆n ≈ 0.8, which is 1 ‒ 2 orders of magnitude larger than conventional refractive

materials32) and k (∆k ≈ 2). This allows wide-range phase and amplitude tuning in many
photonic devices.
Optical lenses are fundamental to displays and imaging32, and the ability to widely tune the
n, k of GO enables many novel forms of optical lenses with nanometer thicknesses and 3D
subwavelength focusing capability17,32,60-62. These features are extremely challenging for
conventional optical lenses that have a limited refractive index contrast. Moreover, GO lenses
also show high stability in harsh environments60 as well as flexibility in tuning the focal
length61. With excellent, robust, and tunable focusing properties as well as facile and scalable
fabrication, these devices are highly promising for practical applications.
An example of a thin GO flat lens32 is shown in FIG. 5d (left). The flat lens, consisting of
alternative sub-micrometer concentric rings formed by alternating GO and rGO regions, was
patterned on a 200-nm-thick GO film via DLW. By virtue of the high index and absorption
contrast between GO and rGO, both the phase and amplitude of the incident beam were
effectively manipulated, allowing 3D subwavelength focusing (λ3/5) below the diffraction
limit. In addition, light focusing across a broad wavelength band from 400 nm to 1500 nm
with an average focusing efficiency of > 32% was also achieved.
The ability to widely tune the n, k of GO also offers new possibilities for holographic
imaging devices in display systems. 3D holographic displays for wide-angle and full-color
images (FIG. 5d (right)) were demonstrated based on multi-level refractive index modulation
of rGO composites achieved with femtosecond optical pulses72. A wide viewing angle of 52
degrees was achieved for static 3D holographic imaging ‒ an order of magnitude larger than
CNT or metamaterial based holograms. Moreover, the spectrally flat variation in n, k also
allows for wavelength-multiplexed holograms for full-colour images. Recently, full color
switchable optical displays were demonstrated based on an anisotropic layered pixel structure
composed of alternating GO/rGO and PDDA layers on a silver-coated substrate74. Direct laser
printing of all primary colors with a diffraction-limited pixel resolution (250 nm) in a large
area (4 inch in diameter) was achieved by controlling the localized n, k and film thickness
using laser photoreduction.
Optical anisotropy
In its 2D form, GO displays an enormous anisotropy in its material properties, as also
observed for 2D PG and TMDCs75-77. To date, most investigations of the anisotropy of 2D
materials have focused on the linear material absorption and refractive index for applications
such as polarization selection and liquid-crystal displays. The anisotropy of other properties
such as the nonlinear optical Kerr coefficient, for example, remains an area of great interest.
Polarization control is fundamental to optical systems78-80, and the huge absorption
anisotropy and low dispersion of 2D materials are attractive for high performance polarization
selective devices with high selectivity and broad bandwidths. As compared with in-plane
polarized light, the absorption of out-of-plane polarized light in 2D GO films is much lower
(FIG. 5e). This difference gradually decreases with increasing film thickness, as the 2D film
evolves towards isotropic bulk-like material. Even for much thicker films (> 200 nm) than
typical 2D materials, GO films can still maintain highly anisotropic light absorption for
polarization-dependent devices81,82. In addition, this absorption anisotropy covers the visible
to infrared regimes, enabling much more broadband polarization selective devices than bulk
materials12,26,81.
Waveguide polarizers based on patterned GO films integrated with doped silica
waveguides12 (FIG. 5f) achieved a broadband and high polarization dependent loss of up to
~53.8 dB across the visible and near infrared regimes. Layer-by-layer self-assembly coating
methods enabled accurate film thickness control, which was combined with lithography and
lift-off to yield control of the film size and location. As compared with state-of-the-art
integrated silicon polarizers80,83,84, GO waveguide polarizers not only have a much broader
operation bandwidth but also feature simple designs with higher fabrication tolerance.
Many macroscopic uses of 2D materials require them to be dispersed and processed in the
fluid phase, highlighted by liquid crystals (LCs)85-87. When there are a sufficiently large
number of anisotropic particles suspended in a liquid medium, a dynamic LC transition can
occur under external stimuli (FIG. 5g), forming the basis for LC displays. For PG with poor
water solubility, the formation of LCs usually needs strong acids88, in contrast to water-based
LCs that are much easier to process. On the other hand, GO can be mass-produced from
natural graphite via oxidation processes, and the hydrophilic OFGs in GO allow for
monolayer exfoliation in water. These provide a viable route to realize carbon LCs in
aqueous media87.
An electro-optic switch based on GO LCs73 is shown in FIG. 5h. Due to several limiting
factors such as the electrophoretic drift, electrolysis of water, and GO reduction, it is usually
difficult to control the alignment of nematic GO by applying electric fields. Song et al.
overcame this by using low-concentration GO dispersions (0.05 vol%), where the interactions
between the anisotropic GO flakes were weak enough to allow both microscopic ordering and
macroscopic alignment of GO LCs under external electric fields. Based on this, electro-optic
GO-LC switches with well-aligned, high-quality GO over large areas as well as with
macroscopic sized electrodes were demonstrated.

Nonlinear optical properties

The ever-increasing demand for data capacity and processing speed has motivated the use
of nonlinear optical devices for optical communications89,90, displays91,92, astronomy93,94, and
quantum optics95,96. The ultrafast nonlinear optical response is highly useful for all-optical
information processing since it avoids the need for slow and inefficient optical-electrical-
optical (O-E-O) conversion, thus resulting in unparalleled processing speed97,98.
Interest in the optical properties99 of 2D materials – both linear and nonlinear ‒ has grown
significantly in the past decade. GO has unique advantages over other 2D materials, with its
relatively large (up to 3.5 eV100) and direct material bandgap that enables broadband
fluorescence for biosensing and molecular detection. It also has an ultrahigh Kerr optical
nonlinearity (about 4 orders of magnitude larger than silicon) and relatively low linear
absorption (over 100 times lower than PG in the infrared regime101), both of which are critical
for nonlinear optical devices. The OFGs in GO can also break the material symmetry to
produce a 2nd order optical nonlinearity, which is not observable in PG because of its
centrosymmetry. In this section, we review the nonlinear optical properties of GO and rGO,
together with their applications. Note that while fluorescence is typically not considered to be
nonlinear, we discuss it here because it also involves a conversion of optical frequencies.
Fig. 6. Nonlinear optical properties and applications. a| Schematic band diagram for fluorescence
process in GO. b| Fluorescence image of tumor cells captured by a GO chip (left) and comparison of
capture yield between the GO chip and a functionalized flat silicon device (right). c| Schematic band
diagram for the saturable absorption (SA) process in GO. d| Left: optical spectrum and temporal
waveform of a mode-locked fiber laser (MLFL) using GO as a saturable absorber; Right: optical
spectrum of a MLFL using rGO as a saturable absorber. e| Schematics showing energy and
wavelength conversion of second harmonic generation (SHG). f| Left: mass histograms for GO
samples, inset shows TEM image of the measured GO sample; Right: multiphoton excited
fluorescence spectrum (blue) of GO with excitation at 800 nm, together with the two-photon-excited
fluorescence spectrum (green). g| Schematics showing energy / wavelength conversion of four-wave
mixing (FWM) process (left) and changes of optical pulses induced by self-phase modulation (SPM)
(right). h| Left: enhanced FWM in a GO-coated integrated MRR; Right: enhanced SPM in a GO-coated
silicon waveguide. Panel b adapted with permission from REF.102, Springer Nature Limited. Panel d
left adapted with permission from REF.103, IOP Publishing. Panel d right adapted with permission
from REF.104, Elsevier Publishing. Panel f adapted with permission from REF.105, Royal Society of
Chemistry. Panel h left adapted with permission from REF.53, Wiley-VCH; panel h right adapted with
permission from REF.106, ACS Publications.
Fluorescence
Fluorescence, where a material absorbs photons with energies above its bandgap and
subsequently radiates photons with energy near the bandgap after the excited photocarriers
relax to lower energy states (FIG. 6a), is used for dyes, biosensing, gemology, medicine,
mineralogy, printing, and many other areas5,107. In contrast to silicon’s indirect bandgap and
PG’s zero bandgap, GO has a direct bandgap typically > 2 eV (FIG. 1b). This, together with
the ability to tune the bandgap via reduction or doping, allows for tunable fluorescence across
a broad band from the ultraviolet to the infrared regimes5,20,108. The broadband fluorescence of
GO, along with its capability of direct wiring with molecules and high dissolubility in
biomedia, has enabled sensitive biosensing and molecular detection109.
GO has been widely used for fluorescent labeling. It has a fluorescence emission peak that
is strongly dependent on the excitation wavelength when immersed in a polar solvent. This
contrasts with organic dyes and inorganic quantum dots where the fluorescence emission
peaks are independent of the excitation wavelength. The fluorescence wavelength in GO is
affected by the giant red-edge effect that breaks Kasha’s rule110, making it highly promising
for near-infrared biological imaging based on two-photon excitation spectroscopy. FIG. 6b
shows an example of using GO for biomolecular detection102, where a microfluidic chip with
functionalized GO nanosheets on a patterned gold surface captured circulating tumor cells
from blood samples of cancer patients. A high sensitivity of 73 ± 32.4% at 3–5 cells per ml
blood was achieved, together with an improved capture yield over comparable functionalized
flat silicon devices.
Although fluorescent, GO can also efficiently quench fluorescence via either charge
transfer or the Förster resonance energy transfer (FRET) effect 107. Interestingly, since GO has
both fluorescence and quenching abilities, it can serve as either a donor or acceptor during the
FRET processes. As a heterogeneous lattice, including both FRET donor and acceptor
molecules on a large planar surface, GO enables different types of biosensors for biomolecule
detection and DNA analysis. For example, fluorescent GO was used as a FRET donor for the
detection of DNA hybridization111, whereas quenching GO was employed as a FRET accepter
for selective and rapid detection of multiple DNA targets112.
Saturable absorption
Saturable absorption (SA), where the light absorption of a material decreases with
increasing light intensity, has been widely used for short-pulsed lasers in industry and
scientific research99,113. Bulk SA materials such as organic dyes, semiconductor saturable
absorber mirrors, and ion-doped crystals have been widely used in commercial short-pulsed
lasers. However, they suffer from limitations with respect to narrow wavelength ranges, slow
recovery times, low flexibility in tuning the SA parameters, and high fabrication costs114. In
contrast, 2D materials that feature broadband absorption and ultrafast recovery times are
proving to be excellent SA materials115. Since the first demonstration of mode-locked fiber
lasers based on SA in graphene in 2009116, there has been an explosion in activity in using SA
in 2D materials for short-pulsed lasers. The fast carrier relaxation times in 2D materials has
also allowed the dynamic SA process to be used for ultrafast all-optical modulation, typically
via pump-probe schemes117,118.
Despite its relatively weak SA compared to PG, mainly due to its non-zero material
bandgap, GO has been used for many pulsed fiber lasers because of its simple fabrication
processes and the ability to tune its SA properties104,119-121. The SA in GO can arise from not
only band-to-band transitions but also from defect states. For example, SA originating from
the ground-state bleaching of the sp2 orbitals has been observed122,123, which had an energy
gap of ~0.5 eV.
The principle of SA in GO is schematically illustrated in in FIG. 6c, showing fundamental
similarities with other 2D materials such as PG and TMDCs. By leveraging both the SA and
polarization selectivity of a GO-coated side-polished fiber in a fiber ring laser, stable mode-
locked pulses (FIG. 6d, left panel) from a mode-locked fiber laser (MLFL) have been
generated103. Switchable operation from mode-locking to Q-switching was demonstrated by
changing the polarization state. A saturable absorber using rGO also resulted in highly stable
mode-locked pulses from a MLFL104 with a repetition rate of ~16.79 MHz and pulse duration
of ~1.17 ps (FIG. 6d, right panel). Recently, SA in GO-coated silicon waveguides was
investigated106, showing increasing efficiency and decreasing power threshold with increasing
film thicknesses.

Second-order optical nonlinearity

The nonlinear response of a material excited by an external optical field (E(t), scalar) can
be expressed as (in scalar form for brevity, and in the dipole approximation) 97
P(t) = ε0 (χ(1) E(t) +χ(2)E2 (t) + χ(3) E3 (t) + …) (1)
where P(t) (scalar) is the light induced polarization, ε0 is the vacuum permittivity, and χ(i) are
the ith-order optical susceptibilities, which generally are tensors of rank (i + 1). In Eq. (1), χ(1)
describes the linear optical properties such as n and k, while χ(2) corresponds to 2nd order
nonlinear optical processes including second-harmonic generation (SHG, FIG. 6e), sum /
difference frequency generation, the Pockels effect, and electro-optic rectification99. In the
dipole approximation, the 2nd order nonlinearity is zero in bulk centrosymmetric materials
such as silica and silicon, although it exists at the surface where the inversion symmetry is
naturally broken, or at the interface between different materials124-126. Note that the
susceptibilities in Eq. (1) are complex, with the real and imaginary parts contributing to
different effects. For example, the real part of χ(1) accounts for linear refractive index, and the
imaginary part of χ(1) is responsible for linear optical absorption.
The 2nd order optical nonlinearity has many applications in both the classical and quantum
regimes, exemplified by optical autocorrelators127, electro-optic modulators128, optical
coherence tomography129, and quantum light sources130. Many 2D materials that lack
inversion symmetry have displayed χ(2) values much higher than bulk materials131,132. Unlike
PG that is centrosymmetric, and hence has no χ(2) unless induced by external excitations that
break the inversion symmetry, GO can have a high 2nd order optical nonlinearity arising from
its highly heterogeneous structure. Efficient SHG from GO has been observed105, where a
large hyperpolarizability of (1.36 ± 0.15) × 1025 esu at 800 nm was obtained by measuring the
molar mass distribution of 2D GO sheets dispersed in an aqueous suspension (FIG. 6f).
Voltage-controlled SHG in a rGO/silicon heterointerface was also demonstrated when excited
by a 1064-nm pulsed laser133, offering new possibilities for integrated photonic devices with a
tunable 2nd order optical nonlinearity.

Third-order optical nonlinearity

In Eq. (1), χ(3) describes the 3rd order nonlinear optical processes that are present in all
materials, in contrast to χ(2) that only exists in non-centrosymmetric materials as mentioned.
The 3rd order nonlinear response gives rise to a rich variety of processes, including four-wave
mixing (FWM), self-phase modulation (SPM), cross-phase modulation (XPM), third-
harmonic generation (THG), two-photon absorption (TPA), SA, stimulated Raman scattering,
and many others. The response represented by Eq. (1) is virtual, or parametric – in other
words, it is a fixed and fundamental property of the material band structure and operates
through virtual excitations. However, processes that involve optical absorption, such as TPA
or SA, can result in real photogenerated carriers which alter the quiescent material nonlinear
response and render Eq. (1) incomplete. Real carrier effects are complex processes not only
generated by, but can induce their own, TPA or SA. They tend to be much slower than the
intrinsic virtual response since they depend on carrier diffusion, recombination, etc. The third-
order parametric processes arising from χ(3), in contrast, operate by virtual excitation of
carriers without creating photogenerated carriers (FIG. 6g), and so are quasi-instantaneous
with ultrafast response times on the order of femtoseconds91. This has motivated ultrafast all-
optical signal generation and processing for telecommunications, spectroscopy, metrology,
sensing, quantum optics, and many other areas89,96.
Nonetheless, despite the success of nonlinear optical devices in optical communications
and information processing97,98,134, particularly those in integrated form, they are subject to
continual research to improve their performance. For example, although silicon is a leading
material for integrated optics, it has very strong TPA in the near-infrared regime, which limits
its nonlinear optical performance in the telecom band. Other CMOS-compatible materials
such as silicon nitride (SiN) and high-index doped silica glass (Hydex)98,135 have a much
weaker TPA, although this comes at the expense of a much lower Kerr nonlinearity than
silicon.
In the past decade, the giant third-order nonlinear optical response of 2D materials has been
widely recognized99,113. Although GO has a Kerr coefficient n2 that is typically 10-14 ‒ 10-13
m2 W-1, which is lower than PG (typically 10-13 ‒ 10-12 m2 W-1), it is nonetheless still 4 orders
of magnitude larger than silicon. This is more than enough for practical devices such as
coated optical fibers or integrated photonic chips. The large bandgap of GO also yields much
lower linear light absorption and TPA in the near-infrared regime than PG, which is very
attractive for nonlinear optical processes where high light intensities are typically used to
enhance the nonlinear response. The nonlinear optical absorption arising from Im(χ(3))
processes such as SA and TPA is dependent on the bandgap of the prepared GO as well as the
wavelength of the excitation light. Since there are different mechanisms and bandgaps for SA
and TPA in GO, they can and often do coexist, leading to very complex and wavelength
dependent nonlinear absorption.
Enhanced FWM in Hydex and SiN waveguides integrated with 2D GO films has recently
been demonstrated101,136, with an improvement in the conversion efficiency of ~6.9 dB for a
uniformly coated Hydex waveguide and ~9.1 dB for a SiN waveguide with a patterned film.
The deposition and patterning of the 2D GO films were realized by layer-by-layer self-
assembly together with lithography and lift-off. These fabrication methods also yielded
patterned 2D GO films integrated onto Hydex MRRs53, where the resonant enhancement
significantly increased the optical intensity in the cavities, increasing the conversion
efficiency by ~10.3 dB (FIG. 6h, left panel). In addition to FWM, enhanced SPM in GO-
coated silicon waveguides was also demonstrated. As compared with Hydex and SiN
waveguides, silicon waveguides have smaller dimensions and consequently a much higher
mode overlap with GO. The hybrid waveguides showed significantly improved spectral
broadening of optical pulses (FIG. 6h, right panel) compared to uncoated silicon waveguides,
achieving a high broadening factor of 4.34 for a 3-mm-long waveguide integrated with a
patterned GO film.

Electronic properties

The electrical conductivity of graphene based materials can be efficiently modulated by

varying the Fermi energy level and material bandgap. It has been observed that GO can transit
from an insulator to semiconductor and then to a semi-metal during the reduction process, as
the bandgap decreases (FIG. 7a)137. Thus, the range in tuning the material transition from GO
to trGO is much larger than what can be achieved by just doping PG138. On the other hand,
trGO is very close to a gapless semimetal ‒ with a Fermi energy level at the Dirac point of the
bandstructure that can shift down or up through chemical doping (FIG. 7a), thus yielding p-
type or n-type doped rGO. The doping process produces a bandgap between the valence and
conduction bands that converts the semi-metal graphene to a semiconductor. Furthermore,
doping modifies the molecular structure, which affects the electrical, mechanical, optical, and
thermal properties of doped rGO.
Chemical doping can be categorized into: 1) substitutional doping, or 2) surface transfer
doping. Here, we mainly focus on substitutional doping by exchanging carbon atoms with
heteroatoms to tune the Fermi energy level of rGO, where covalent bonds link the doped
atoms to the carbon network. This approach has been used to realize metalloids and non-
metals incoporating B, N, P, S, F, Cl, and Si, which form either p-type or n-type doping,
depending on the number of valence electrons of the dopant. For example, since B has fewer
valence electrons, it produces holes in valence band, thus downshifting the Fermi energy level
to form p-type doping (FIG. 7b). In comparison, N and P provide extra electrons in the
conduction band, thus upshifting the Fermi energy level to from n-type doping. As a result,
the conductivity of rGO can be tuned by adjusting the type and concentration of the doping.
The ability to tune its electrical properties has enabled many electronic devices based on
rGO. Combined with the ability to pattern the material conductivity via laser photo reduction,
this has been used for microheater electrodes (FIG. 7c)40. By reducing the thickness of rGO
to decrease its light absorption, patterned rGO can also serve as transparent conductive
electrodes for light emitting diodes (LEDs) (FIG. 7d)139 and solar cells140. For LEDs, since
only the laser exposed areas are conductive, it enables patterned lighting. Further, it is also
possible to achieve incandescent light emitters based on rGO “papers” composed of
monolayer rGO and single walled CNTs (FIG. 7e). This system can withstand high
temperatures up to 3000 K141 – substantially higher than pure CNTs or rGO, and most
importantly, with a lighting efficiency comparable to tungsten wires. Due to the ultrathin
freestanding design, these rGO “papers” are bendable and lightweight, useful for wearable
electronics and fast heating.

Fig. 7. Electronic properties and applications. a|Tuning the bandgap of GO by reduction. b| Tuning
the Fermi energy level of rGO by different types of doping. c| AFM image of a rGO microheater.
d|Optical microscopy image of rGO used as transparent electrode on LEDs. e| Photos of a rGO light
emitter. f| A photo of a GO/rGO supercapacitor. g| 3D conceptual drawing and photo of a rGO
sensor. h| SEM image of a rGO transistor. Panel c adapted with permission from REF.40, Elsevier
Publishing. Panel d adapted with permission from REF.139, ACS Publications. Panel e adapted with
permission from REF.141, Wiley-VCH. Panel f adapted with permission from REF.142, Springer Nature
Limited. Panel g adapted with permission from REF.143, Springer Nature Limited. Panel h adapted
with permission from REF.144, Springer Nature Limited.
Porous rGO has a high conductivity and large surface area that are both ideal for
electrochemical energy storage (FIG. 7f)142. For laser-patterned GO films, the unexposed or
unreduced areas remain insulating, which can be used as an in-plane electronic insulator for
interdigital supercapacitors that have achieved high power and energy density10. The porous
structure also exhibits a significant change in conductivity as a result of applied external
pressure, which has been used for realizing pressure sensors (FIG. 7g) with high sensitivities
over a wide range of pressure143. In addtion, the high stability and mechanical strength of GO
as well as its low electrical conductivity have been exploited for anti-self-discharge seperation
in lithium-sulfur batteries145.
Recent progress in microwave reduction methods have shown that the electrical properties
of rGO can be made extremely close to that of PG, and so field effect transistors (FETs) based
on rGO have been demonstrated11 and used for detecting human papillomavirus (HPV) (FIG.
7h)144, proving the viability of these devices for clinical applications.

Optoelectronic properties
External electrical fields can not only alter the optical response of GO and rGO, but the
reverse is true ‒ light excitation can modify their electrical response, and this interplay forms
the basis for optoelectronic devices. In addition to distinct optical and electronic properties,
GO and rGO also exhibit remarkable optoelectronic properties. In this section, we summarize
them and review their applications.
Fig. 8. Optoelectronic properties and applications. a| Schematic band diagram for
electroluminescence process in GO. b| Light emission from a GO-/rGO-based light-emitting diode
(LED) (left) and luminescence spectra for varied gate bias from 0 to 50 V (right). c| Schematic
showing photocurrent generation in rGO induced by an external electrical field. d| Schematic
illustration of a photodetector (PD) based on rGO-silicon nanowire array (SiNW) heterojunctions.
Inset shows a photograph of the fabricated device. e| Schematic illustration of light-excited charge
transfer in GO or rGO. CB: conduction band. VB: valence band. f| Left: color variation of GO
suspension during photocatalytic reaction under mercury-lamp irradiation: i) before irradiation, ii)
start of irradiation, iii) irradiation for 30 min, iv) irradiation for 2 h; Right: Photocatalytic methanol
formation rate (RMeOH) on different GO samples (GO-1, GO-2, GO-3) and TiO2 under visible light
irradiation. Panel b adapted with permission from REF.146, Springer Nature Limited. Panel d adapted
with permission from REF.147, Wiley-VCH. Panel f left adapted with permission from REF.148 , Wiley-
VCH; Panel f right adapted with permission from REF.149, RSC Publishing.

Electroluminescence
Electroluminescence, where electrons are excited by external or build-in electrical fields
and subsequently radiate photons when they return to the low energy state, is similar to
fluorescence except with a different excitation mechanism. A typical example of
electroluminescence is LEDs, which are key components in the display industry. The light-
emitting mechanism of LEDs is different to that of incandescent light sources such as
tungsten filaments and the rGO light emitter mentioned in FIG. 7e, which can result in
significant benefits in energy consumption, lifetime, device footprint, and switching speed.
The large and tunable bandgap of GO, together with its tunable electrical conductivity and
high thermal conductivity, has been used to realize high-performance LEDs. A GO / rGO-
based field-effect LED146 is shown in FIG. 8b. The light emission was based on semi-reduced
GO formed at the rGO / GO interface created via laser scribing. The rGO nanoclusters in the
semi-reduced GO interfacial layer have a range of sizes, resulting in different discrete energy
levels that allow selective excitation of luminescence by electrical gating or changing the
doping level. Tunable electroluminescence from blue to red was achieved, with a brightness
of 6,000 cd m-2 and an efficiency of ~1 %. Further, the high thermal conductivity of rGO has
been exploited for heat removal in integrated gallium nitride (GaN) LEDs150, which
significantly improved the heat dissipation performance, resulting in a much lower junction
temperature and thermal resistance compared to devices without GO.
Photovoltaic effect
The photovoltaic effect is the generation of voltage or current in an irradiated material. The
principle of photovoltaic photocurrent generation in rGO is schematically illustrated in in
FIG. 8c, where the photo-generated electron–hole pairs are separated by an external electrical
field.
An important application of the photovoltaic effect is photodetectors (PDs), particularly in
the context of 2D materials151. PDs play a key role in optical communications, sensing,
imaging, astronomical detection, and environmental monitoring151,152. Although conventional
PDs based on bulk materials (e.g., Ge, Si, and InGaAs) are mature, their response speed,
detection efficiency, and operation wavelength range can always be improved to meet ever-
increasing performance demands. Graphene-based PDs have attracted significant interest over
the past decade because of their wavelength-independent absorption arising from the zero
bandgap as well as their ultrafast response enabled by high carrier mobility153-157. This has
resulted in superior performance compared to bulk-material-based PDs. In contrast to
unreduced GO where the light absorption and electrical conductivity are both too low for
PDs, trGO has material properties that are close to graphene, which have enabled many rGO-
based PDs with performance comparable to graphene-based PDs147,158-170. In addition, rGO
has unique advantages for mass producibility, compatibility with diverse substrates, and
flexibility in material engineering, making it attractive for manufacturable PDs.
 A PD implemented by rGO-silicon nanowire array formed by self-assembly147 is shown in
FIG. 8d. The broadband response of rGO resulted in a PD operating from the visible to the
terahertz (THz) regime, reaching a maximum photoresponsivity of 9 mA/W in the mid-
infrared regime. With a high sensitivity to detect mid-infrared radiation from the human body,
this PD is attractive for human infrared sensors. Another rGO PD has achieved an ultrahigh
photoresponsivity of 3.1 × 104 A/W, together with a remarkable external quantum efficiency
(EQE) of 1.04 × 107 %166. The photoresponsivity was about four orders of magnitude higher
than comparable graphene devices, with the EQE outperforming commercial silicon PDs.
This high performance resulted from the specially designed 3D nanoporous structure of rGO,
which showed > 40 times higher light absorption than graphene, together with an electron
mobility that was over a hundred times higher than rGO films formed from nanoflakes.
The photovoltaic effect has also been utilized in solar cells that convert solar energy into
electrical power171, in contrast to solar absorbers mentioned previously that use solar thermal
energy to drive heat engines. Polymer composites incorporating functionalized GO sheets
have been employed as a photoactive layer in organic photovoltaic cells172, achieving a
maximum energy conversion efficiency of 1.4 %. Photoactive layers formed by polymers
incorporating rGO quantum dots were also investigated, showing significantly improved
photovoltaic performance compared to photoactive layers formed by rGO sheets173.
Photoconductivity
Photoconductivity, also termed the photogating effect 151, is based on light-induced charge
transfer (FIG. 8e) that changes the carrier density and consequently the material conductivity.
An important application of the photoconductive effect is photocatalysis, which has a long
history and has experienced significant development in the past 50 years. Photocatalysts drive
chemical reactions by absorbing light to induce charge transfer, and so GO, with its
broadband absorption and excellent semiconductor properties, is attractive as a nontoxic
photocatalyst with high efficiency.
The use of GO as a semiconductor photocatalyst for producing hydrogen via water
dissociation has been achieved148, where moderately oxidated GO steadily catalyzed the
generation of hydrogen from an aqueous methanol and pure water solution under ultraviolet
or visible irradiation (FIG. 8f, left panel). Photocatalytic conversion of carbon dioxide to
methanol based on GO has also been realized149, with a high conversion rate of 6 times that of
titanium dioxide (TiO2), a conventional photocatalyst, under visible irradiation (FIG. 8f,
right panel).
Other applications
Either in its pristine form or a reduced form, GO has underpinned many other technologies
related to photonics, electronics, and optoelectronics. They generally leverage GO’s chemical
or physical properties such as its high hydrophilic nature, strong capillary action, high
surface-to-volume ratios, and the electronic and optical properties mentioned above. Some of
these technologies have already become widely successful on a large scale and are
summarized in Table 1. We discuss these next.
Photothermal therapy is commonly used in cancer treatment with minimal invasiveness,
high specificity, and low toxicity. It relies on the activation of photothermal agents taken up
by cells via light absorption, thus generating heat that kills cancer cells via thermal ablation.
The photothermal agents usually absorb strongly in the near-infrared regime whereas normal
cells in healthy tissues do not. With strong near-infrared absorption and high photothermal
efficiency, GO and rGO in the form of nanoparticles have been demonstrated to be high
performance photothermal agents174-176. As abundant materials that can be synthesized from
graphite, they are also inexpensive compared to other photothermal agents such as gold-based
nanoparticles177. Polyethylene glycol (PEG) coated GO was first used for in-vivo
photothermal therapy174, achieving ultra-efficient tumor ablation in mice without obvious side
effects. Subsequently, rGO nanosheets with noncovalent PEGylation, which had more than 6
times higher absorption in the near-infrared regime than nonreduced, covalently PEGylated
GO, were employed for selective photoablation of cancer cells175. Photothermal treatment of
Alzheimer’s disease based on functionalized GO has also been achieved176, where GO
modified by thioflavin-S (ThS) effectively dissociated amyloid deposits in mice cerebrospinal
fluid after near-infrared irradiation.
Table 1 | Summary of other typical applications of GO and rGO.
Materials Applications Materials properties Main feature Ref.
176
GO Photothermal 1. Strong optical absorption to Remarkably reduced side effects and
therapy generate local heat improved selectivity compared to
2. High dissolubility in biomedium chemotherapies and radiotherapies
178
rGO Protective coatings 1. Optically transparent 1. No detectable permeation of
2. Extremely low permeation of hydrogen and moisture for a 30-nm-
gases and liquids for multilayer thick films
rGO films 2. No detectable permeation of all
3. High stability and little toxicity tested gases and liquids for the films
thicker than 100 nm
4. Solution-based fabrication for
large-scale manufacture
GO Molecular and Ionic 1. Well-defined nanometer pores 1. Blocking solutes with radii > 4.5 Å 179
sieving 2. Low frictional water flow 2. High permeation rate thousands of
3. High surface-to-volume ratio times faster than simple diffusion
4. High pressure inside the
capillaries
GO Antibacterial agent 1. Strong dispersion interactions Green antibacterial material with 180
and nanotoxicology with lipid molecules little bacterial resistance
2. Destructive extraction of
phospholipids from the cell
membranes to reduce bacteria
viability.
GO Paper production Unique interlocking-tile 1. Outperforming traditional carbon- 16
arrangement of GO nanosheets in and clay-based papers in stiffness and
a near-parallel fashion enabled by strength
directed-flow assembly 2. With chemical tunability for
diverse applications

Protective coatings to guard against corrosion, mechanical wear, fouling, and

microorganisms are integral to many industries such as food, medicine, electronics,
chemicals, and military181. In contrast to conventional metal coatings or organic paint that
often have hazardous constituents with negative environmental impact, GO and rGO can
serve as low-cost and eco-friendly protective coatings that also have excellent gaseous
impermeability, anti-bacterial property, adsorption capacity, visible light transparency,
mechanical strength, and thermal stability. High performance impermeable barrier films based
on chemically reduced GO films have been reported178. For the 30-nm-thick films that are
optically transparent, no hydrogen or moisture permeation was detected, while for > 100 nm
thick films, all tested gases, liquids, and aggressive chemicals were blocked with no
detectable permeation.
Molecular and ionic sieving based on thin membranes that allows fast separation of solutes
in aqueous media has a key role in water purification and desalination as well as substance
detection and filtration. Ultrasmall GO membrane pores on nano or sub-nano scales display a
high capillary pressure. This, along with the large surface-to-volume ratios, is extremely
effective as molecular and ionic sieves179,182-184. GO membranes with a thickness of 1.8 nm
achieved extremely high hydrogen separation selectivity of 3400 and 900 for H2/CO2 and
H2/N2 mixtures, respectively182. Molecular sieves based on micrometer-thick GO laminates
were also demonstrated, which blocked all solutes with radii >4.5 angstroms in water, at
permeate rates thousands of times higher than normal diffusion179. Subsequently, zeolitic
imidazolate framework-8 (ZIF-8)-nanocrystal-hybridized GO membranes were demonstrated
to have an ultrahigh water permeability of 601 m−2 h−1 bar−1 – a 30-fold increase over
comparable pure GO membranes18. The strong molecular sieving capability of GO
membranes was also used for highly sensitive substance detection based on the changes in
GO’s optical or electrical properties after absorption of target gases or organic
compounds183,185. In addition, reversible fusion and fission in GO fiber shells induced by
solvent evaporation and infiltration were observed recently186, making GO an attractive
material for constructing dynamically transformable systems.
Biomedicines for drug delivery, disease diagnosis, and controlled drug release are an
important application of nanomaterials. In the past decade, the excellent antibacterial
capability of GO and GO composites has been widely recognized. It has been demonstrated
that GO exhibits better antibacterial performance than rGO and graphite187. More importantly,
since its antibacterial action is based on physical damage, GO based antibacterial agents have
low toxicity and little bacterial resistance. It has been observed that GO nanosheets can
interfere with bacteria and disrupt their cell membranes188. It is also found that GO nanosheets
can also induce destructive extraction of phospholipids from Escherichia coli and
consequently greatly reduce their viability180.
Finally, GO has also been widely exploited for paper production16,189. GO papers made
from GO nanosheets in an interlocking-tile arrangement have a significantly improved
mechanical stiffness and strength as compared with traditional papers 16. The mechanical
strength of GO paper materials can be improved even further by modifying GO to incorporate
divalent ions such as Mg2+and Ca2+190. The combination of simultaneously achieving a free-
standing paper with antibacterial capability has resulted in high-performance GO antibacterial
papers191. Insulating GO papers can also be converted to electrically conductive rGO papers
via thermal annealing or chemical reduction192,193.

Future prospects

We have reviewed recent advances in GO based photonics, electronics, and optoelectronics,

clearly showing that this promising interdisciplinary field has progressed tremendously in the
past decade. Despite this, though, there is nonetheless still significant room for new
innovations and improvement. In this section, we conclude this Review by discussing these
open challenges as well as future prospects for establishing certification standards and
synthesis protocols, improving material quality, theoretical modelling, and opening up new
applications. These issues are intimately connected, and their synergy will underpin future
technogies based on GO photonics, electronics, and optoelectronics.

Certification standards and synthesis protocols

As shown in FIG. 9, increasing the degree of reduction increases the electrical conductivity
of rGO for a diverse range of electronic applications that require the conductivity to be varied
by orders of magnitude. For example, transistors144 and transparent electrodes57 require the
highest conductivities (typically ~106 S/m), whereas most sensors143 and microheaters40 only
need a much lower conductivity. In comparison, when using GO as separators of structural
capacitors194,195 an extremely low conducitivity is required to provide high electrical isolation.
This also applies to interdigital microsupercapacitors where unreduced GO acts as in-plane
seperators142. On the other hand, the optical properties of rGO, such as the refractive index n
and extinction efficient k, both increase with the degree of reduction. Similar to electronics,
photonic applications of GO require a range of properties. For example, solar absorbers51
require high light absorption, and thus trGO is more suitable. The same is true for PDs147,167
that require both high light absorption and conductivity to generate strong photocurrents. In
addtion, a high absorption and/or refractive index contrast between the reduced and
unreduced regions are beneficial for flat lenses32,60-62 and holograms74,196 to widely vary the
amplitude and phase. Fluroscence148 and photocatalyst51 applications mainly utilize the
semiconductor properties of semi-reduced GO. Finally, in order to minimize the loss of
waveguide devices or spacial-light polarizers12,26, highly oxidized GO films are critical since
they are pure dielectrics with minimal absorption. In summary, there is not one set of criteria
suitable for all applications, but rather the entire family of graphene based materials is highly
useful due to their high flexibility and tunable properties. GO and rGO signfiicantly increase
the variety of graphene based technologies and devices that can be realized, well beyond that
of simple PG.
The recent growth in the field of GO based devices has significantly advanced industrial
scale applications of graphene family materials. To this end, establishing large-scale cost-
effective synthesis methods and widely recognized certification standards are critical. The
molecular structure of GO films can be quantified by a few key parameters that include the C-
O ratio, the ID/IG and I2D/IG ratios, flake sizes, and layer numbers. The C-O ratio, which can
be measured via XPS, is a key parameter to quantify the reduction degree of GO11,67 ‒ the
lower the C-O ratio, the lower degree of reduction. Second, the ID/IG and I2D/IG ratios, which
can be obtained from Raman spectroscopy11, are widely used to characterize the properties of
graphene family materials. The ID/IG ratio provides a good indication of the defect density of
GO/rGO materials ‒ the lower the ratio, the lower the defect density. The I 2D/IG ratio reflects
the formation of graphene domains ‒ the higher the ratio, the closer to PG. Lastly, the flake
sizes in the GO films can be measured via SEM and the layer numbers determined by
measuring the film thicknesses via AFM17.

Fig. 9. Diverse applications of GO with different degrees of reduction. srGO: semi-reduced GO.
trGO: totally reduced GO. Insets in the top row from left to right are adapted with permission from
REF.12 (Wiley-VCH), REF.102 (Springer Nature Limited), REF.148 (Wiley-VCH), REF. 51 (Springer Nature
Limited), REF.51 (Springer Nature Limited), and REF.147 (Wiley-VCH), respectively. Insets in the bottom
row from left to right are adapted with permission from REF.142 (Springer Nature Limited), REF.143
(Springer Nature Limited), REF.40 (Elsevier Publishing), REF.141 (Wiley-VCH), REF.144 (Springer Nature
Limited), and REF. 57 (Springer Nature Limited), respectively.

For applications requiring both low electrical conductivity and optical absorption, it is
preferable to use GO films with a low C-O ratio, in the range of 1:4 to 1:132,36,61, which also
results in high ID/IG and low I2D/IG ratios. On the other hand, for applications requiring a high
electrical conductivity57,144 or optical absorption51,197, the requirements are the opposite. The
measured film electrical conductivity and optical absorption can also be used to quantify the
degree of reduction of the GO material. In addition, in order to fabricate smooth GO/rGO
films, monolayer GO flakes with sizes on the order of 100’s nm are needed17. For more
specialized applications, such as conformal coating over nanostructured surfaces including
slot waveguides198 or any nanostructures with a small gap size (< 100 nm), the GO flake size
should be reduced even further70.
Since the material properties of GO and rGO are affected by the fabrication methods, the
quality and consistency of synthesized materials in practical settings vary widely, which has
limited its large-scale industrial applications. In order to overcome this challenge, it is
necessary to develop synthesis protocols. Liquid phase exfoliation is attractive for mass
producing GO flakes from natural graphite, which can produce GO in quantities of tons199.
The exfoliated GO flakes can be further used for either solution based applications or for film
coatings. The reaction during the exfoliation process needs to be properly controlled in order
to obtain the desired degree of reduction, which can be quantified by the C-O ratio as
mentioned before. So far, the most effective method for producing highly oxidized GO flakes
is the modified Hummer’s method24, which is able to produce monolayer flakes with a high
oxidation extent of up to 69 % .
For thin films, the synthesis protocols should include two addtional steps ‒ film synthesis
and GO reduction. To synthesize GO films in industrial scale, it is necessary to achieve fast,
large-scale, and roll-to-roll production. For energy storage and most electrical applications
that do not require accurate thickness control, the Dr. Blade method allows roll-to-roll
production of GO films with thicknesses of a few microns27. On the other hand, most
photonics based applications require very accurate thickness control down to a few
nanometers (~1/100 of the optical wavelength). In this case, the appropriate approach is the
solution based layer-by-layer self-assembly method12,51,53.
For the reduction of GO films, methods based on electromagnetic wave exposure (using
light or microwaves) usually produce higher quality films than thermal or chemical reduction
methods, and are also fast and efficient. For large-scale homogeneous reduction, microwave
methods produce the material with the highest quality that approaches PG, but suffer from
limitations in terms of film patterning and control of the degree of reduction. In contrast,
photoreduction methods, including flashlight 67 and laser reduction37, show excellent
capabilities in these aspects, although they have thus far not been able to achieve the same
level of material quality as that of microwave reduction. Therefore, in principle the
combination of both microwave and photoreduction methods may yield the optimal approach.
Indeed, microwave reduction requires a pre-reduction11 to increase the conductivity of the GO
films, and so in principle it would be feasible to use either laser or flashlight exposure to
complete the pre-reduction process instead of the typically used hot plate method. This would
allow rGO devices to be fabricated and patterned with a very high film quality approaching
that of PG. Alternatively, the process can be reversed, with laser ablation51 to post-pattern
large areas of microwave reduced GO films, which combines the advantages of microwave
reduction with laser ablation patterning. Conventionally, laser patterning is carried out in a
direct writing, or point-by-point manner, by scanning a single focal spot, thus signficantly
limiting the overall processing speed. The development of multifocal parallel laser printing200
can significantly increase the speed by more than two orders of magnitude, making it
attractive for industrial scale applications. Finally, these hybrid approaches, based on a
combination of both optical and microwave reduction methods, are energy efficient, fast (on a
timescale of a few seconds) and green (not involving or producing any toxic chemicals).
In summary, we believe that the most attractive methods for GO based device fabrication
will involve synthesis protocols that combine the modified Hummer’s method with roll-to-roll
film synthesis, including Dr. Blade coating and layer-by-layer self-assembly, together with
film reduction and patterning methods that combine the advantages of optical and microwave
techniques.

Material quality

Table 2 compares the state-of-the-art performance of GO, rGO, and graphene devices for a
range of applications including electronic, photonic, and optoelectronic devices that
incorporate solid films. For solution-based applications such as fluorescence or
photocatalysis, GO and properly reduced GO show much better performance than graphene
due to their higher solubility and better ability to be processed in water and polar solvents. In
Table 2, we see that the carrier mobility of rGO has improved considerably in the last 10
years201, with current results being only about an order of magnitude lower than PG. Further
improvement would make rGO more suitable for FETs and transparent electrodes. To date,
for many uses such as solar light absorption, polarization selection, mode-locked lasers,
thermal harvesting, and photo detection, GO and rGO devices have already shown
comparable or even better performance than graphene devices. With its highly heterogeneous
structure, GO outperforms centrosymmetric graphene in areas that are based on second-order
nonlinear optical processes. For applications based on third-order nonlinear optical processes,
they each have advantages and disadvantages. Although GO has a smaller optical nonlinearity
than graphene, its significantly lower linear loss is very advantageous for nonlinear optical
processes, and its lower nonlinear loss (e.g., two-photon absorption) is also beneficial at the
high light intensities typically employed in these devices. The adjustable reduction of GO
provides a way to properly balance the trade-off between optical nonlinearity and linear /
nonlinear loss in order to optimize the device performance.
Table 2 | Comparison of the state-of-the-art performance of GO, rGO, and graphene devices for
electronic, photonic, and optoelectronic applications.
Key performance
Application GO rGO a graphene Refs.
parameter

Carrier mobility
Electrodes or FETs ~0 ~ 103 ~ 104 ‒ 105 5,11,22,202
(cm2 V-1 s-1)

Solar absorbers kb <0.01 1.95 2.0 12,17,51

Broadband polarization Extinction ratio (dB) 53.8 27

‒c 12,75
selective devices Operation band (nm) 632‒1600 488‒1650

2nd order nonlinear χ(2)

1.36 × 10−25 ‒c ~0 99,105
optical processes (esu)

3rd order nonlinear n2

1.5 × 10−14 -5.4 × 10−14 -8.0 × 10−14 101,136,203
optical processes (m2 W-1) b

Mode-locked lasers and Nonlinear absorption

-6.2 × 10−8 4.3 × 10−8 9.0 × 10−8 d 106,203,204
all-optical modulation coefficient (m W-1) b

Thermal harvesting Thermal conductivity

8.8 2000 ‒ 4000 ~ 5000 28,205,206
and heat removal (W m-1 K-1)

Photoresponsivity (A W−1)e ~ 1.5 ~ 1.0

Broadband PDs N. A. f 156,167
Operation band (nm) 365 ‒ 1200 500‒3200
a Here we show the state-of-the-art values for highly or totally reduced GO.
b Here we compare typical measured values at 1550 nm.
c There are no reported works on this so far.
d Here we show the measured value for undoped graphene. The nonlinear absorption of graphene can be changed by doping or
introducing defects.
e Here we show and compare the performance of chip-scale integrated PDs incorporating rGO and graphene.
f N.A.: not applicable. GO is a dielectric that cannot be directly used for photo detection.

Given the close relationship between GO and graphene, the efficient production of high-
quality graphene from mass-produced GO is fundamental to many applications. This has been
a driving force since the discovery of graphene, but it is only in the past decade that exciting
progress has been made, with the gap between the properties of rGO and PG being greatly
reduced by the methods based on wet chemistry22 and microwave reduction11. Advancing
these methods further to achieve high-efficiency production at scale, together with precise
patterning of the reduction area and fine control of the reduction degree, will be key subjects
of future work. The first is important for the large-scale manufacture of GO devices for
industry, while the latter two are critical for optimizing the material properties and device
performance.
Reducing the linear optical absorption of GO is critical for many applications, particularly
those based on nonlinear optical processes such as the Kerr effect, FWM, and THG.
Theoretically, one might expect that there is no linear light absorption in the near infrared
regime for pure GO since it has a bandgap > 2 eV. However, there are several factors
contributing to the non-zero loss of practical GO films. These mainly include 1) scattering
loss due to film surface roughness and imperfect contact between adjacent layers, and 2)
linear light absorption induced by localized defects as well as foreign impurities. The
important point, however, is that, since the linear loss from these sources largely stems from
the material growth and fabrication processes, it is not a fundamental property. Hence, there is
a significant potential to reduce the loss even further than the current state-of-the-art GO
hybrid waveguides, that already have propagation losses that are two orders of magnitude
lower than comparable graphene hybrid waveguides12,53,106,136.

Theoretical modelling

The exact chemical structure and fluorescence mechanisms of GO have been debated ever
since the early work in this field5 and this is still the case, although progress has been made,
including new theoretical models that have been proposed to explain experimental
observations207-213. The challenges mainly come from the non-stoichiometric heterogeneous
structure of GO as well as its dependence on preparation processes. The heterogeneous
structure of GO also enables the coexistence of different linear and nonlinear processes.
Balancing these processes to optimize the performance for different applications requires a
more in-depth understanding as well as more precise engineering of GO’s material properties,
which will be greatly assisted with better nano-characterization techniques.
Despite the advances in devices based on the nonlinear optical properties of GO and rGO,
they are mainly semi-empirical and lack in-depth theoretical modelling. Many physical
insights are yet to be explored, such as the source of anisotropy in either n2 or the nonlinear
absorption, the interplay between the different nonlinear absorption mechanisms (e.g., TPA
and SA), the dispersion of the optical nonlinearity, and the interaction between χ(2) and χ(3)
processes. Given its outstanding capability for achieving highly precise on-chip integration
with mature fabrication technology, investigating GO in this form offers a promising avenue
for investigating its material properties. In turn, this will enable integrated devices with new
functionalities and improved performance.
 In order to further control and optimize the material properties of rGO , it is necessary to
understand and theoretically model the reduction process, such as how electromagnetic (either
microwave or optical) waves interact with GO to reduce it. Empirically, molecular dynamic
simulations can visualize the structure evolution, while first principles simulations can shed
light on how the electromagentic energy is absorbed by specific bonds in order to dissociate
them and remove the OFGs. The electromagnetic power, polarization, wavelength, optical
pulse duration, or whether it is pulsed or continueous wave, are important parameters that
govern this process.
Molecular dynamic simulations can simulate the structural evolution during thermal
reduction by applying a static heat field45, which predicts the final C-O ratio and molecular
structure after reduction. To date, there have not been any molecular dynamic simulations of
the reduction of GO films via microwave or photoreduction. The key challenges are how to
apply a fast alternating electromagnetic field in the simulation and to accurately model how
different covalent bonds respond to this field, given that different bonds have unique binding
energies and so will respond differently. First principles simulations214 have shown that
extremely short femtosecond laser pulses (< 5 fs) can effectively remove OFGs without
heating up the graphene network and thus generating defects. However, these ultrashort
pulses are challenging to experimentally achieve and so it is of more interest to simulate the
reduction process with standard pulse widths (e.g., 100 fs). Some theoretical and experimental
work has demonstrated that the shape of femtosecond pulses can enable laser controlled
chemical reactions to manipulate the end products215. Although laser controlled chemical
reactions so far have only been used in gas reactions, the principle of controlling the reaction
paths can be applied to the reduction of GO. This will open up new possibilities for the
selective removal of particular OFGs, which can then be used to further tailor the properties
of rGO films for new applications. So far this has only been acheived with conventional
chemical reactions using toxic chemicals216. In order to realize this ambitious goal, an in-
depth understanding of GO reduction via electromagnetic waves will be critical.

New applications

Improving the performance of current devices will naturally open up new applications. For
example, by increasing the level of SPM in GO hybrid waveguides, broadband super-
continuum generation may be achievable. This could be realized by tailoring the waveguide
dispersion for phase matching over a broader wavelength range. Another example is
achieving broadband ultrafast all-optical modulation by using the SA of GO. Owing to the
broadband SA response of GO, the pump and probe wavelengths can differ by hundreds of
nanometers, which is extremely challenging for lithium niobate modulators or integrated
silicon modulators that have typical operation wavelength ranges of < 100 nm128,217. For
quantum optical applications, entangled photons generated from enhanced 2 nd or 3rd order
nonlinear optical processes such as SHG, THG, and FWM in GO based devices can be
exploited to facilitate quantum optical information processing 95,218.
GO offers new possibilities for the combination of optical micro-combs and 2D materials
to achieve new functionalities. Optical micro-combs are a key technology that has enabled
many breakthroughs90,219-221. However, the challenges to achieve high parametric gain and
self-starting and robust mode-locking significantly limit their performance for practical
applications. Since the first demonstration of gate tunable optical micro-combs incorporating
graphene222, the micro-comb research community has recognized the strong potential of 2D
materials to address these challenges. With its ultrahigh n2 as well as the relatively low linear
and nonlinear loss, GO is promising for enhancing the parametric gain and improving the
comb conversion efficiency (FIG. 10a). The SA in GO could also be utilized for simple
passive mode locking. Several key issues to address in future work include lowering the linear
loss of GO films, accurate dispersion engineering, and achieving the proper balance in the
trade-off between increasing the Kerr nonlinearity while limiting any increase in the linear
loss.
Since GO has an ultrahigh optical nonlinearity, it can also be used for implementing high
performance nonlinear optical fibers, which have applications in fiber pulsed lasers, sensing,
and all optical signal processing223. The state-of-the-art in this area mainly implements GO
films by coating optical fibers on their facets or laterally on planarized surfaces103,104.
However, the nonlinear performance of these devices is limited by the weak light-GO
interaction arising from either a short interaction length or weak mode overlap. Recently, the
direct growth of 2D MoS2 films onto the internal walls of silica optical fibers has been
realized using capillary pre-deposition followed by chemical vapor deposition (CVD) 224. This
will inspire the future fabrication of nonlinear optical fibers with embedded GO and rGO
(FIG. 10b), which would significantly enhance the light-GO interaction and hence the
nonlinear performance. Given the excellent water solubility and self-assembled capability of
GO nanoflakes, similar capillary filling methods can be used for coating GO films on the
internal fiber walls. In this case the fabrication would be even simpler since it would not need
subsequent CVD processes, and the coated GO films could be reduced further to form rGO.
 In its 2D form, heterogeneous GO can form Van der Waals heterostructures that feature
new properties225,226. By stacking 2D GO films with other 2D materials (FIG. 10c), charge
redistribution, interface strain, and structural modifications could be introduced, thus leading
to many extraordinary phenomena. Although this field is still emerging compared to bulk GO
composites, it will likely see significant activity in the next decade.

Fig. 10. Future applications. a| Optical micro-comb generation and mode locking based on a GO-
coated integrated microring resonator (MRR). b| Silica optical fibers with embedded GO and rGO on
the internal walls. c| GO 2D Van der Waals heterostructure. d Electrically tunable rGO devices with
feedback from a detector. C: control circuitry. V: voltage source. e| Terahertz detection and emission
based on rGO films.
 Due to the high conductivity of rGO, it is possible to dynamically tune its response by
applying an external voltage to a conductive coating on a substrate (FIG. 10d). In addition, it
is possible to use detectors (e.g., PD, thermal camera or optical camera) to monitor the
photocurrent output and compare with the designed modulation for calibration. Thus,
electrically tunable rGO devices can be realized to optimize the device performance.
Current GO and rGO optoelectronic devices operate mainly at visible and infrared
wavelengths. In contrast, the THz regime, which is highly relevant to spectroscopy, imaging,
communications, and astronomy227, remains less explored. In principle, rGO with a bandgap
on the order of 10’s of meV can be used for THz wave detection. In addition, it can also be
used as a source for THz wave emission after absorbing photons with energies larger than its
bandgap (FIG. 10e). Although many high-performance THz modulators, detectors, and
emitters based on graphene have been demonstrated 228-230, the use of rGO for THz
applications is still in its infancy147,231. A key challenge is to accurately control the material
bandgap when it is less than 0.1 eV. This places stringent demands on the material fabrication
and characterization methods.
Given the flourish of graphene plasmonics in the past decade 232,233, the use of rGO for
plasmonic based technologies is another attractive field, not only from the perspective of the
mass production of graphene from GO but also from the new features enabled by localized
defects and engineered OFGs.
From an engineering and practicality viewpoint, success in the laboratory at accurately
controlling the layer number and position of GO and rGO films has been fueling
breakthroughs that will enable mass producible GO films for large scale integration in high-
tech industrial sectors, particularly in photonics, electronics, and optoelectronics. The
potential of GO films to enhance the performance of nonlinear optical devices such as Kerr
microcombs is significant.234-291 With the continual accumulation of knowledge of GO’s
material properties, recent progress in device designs,292-298 continued advances in material
synthesis, fabrication, and characterization technologies, 299-300 it is anticipated that major
breakthroughs will continue, further bridging the gap between theory and practice and paving
the way to deliver the promises of that low-dimensional carbon materials offer.

Competing interests

The authors declare no competing interests.

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