Materials Science and Engineering B 220 (2017) 44–58

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Materials Science and Engineering B

journal homepage: www.elsevier.com/locate/mseb

Graphene field emitters: A review of fabrication, characterization and

properties
Leifeng Chen a,b,⇑, Hu Yu a, Jiasong Zhong a, Lihui Song a, Jun Wu c,⇑, Weitao Su a
a
College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018, PR China
b
State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027, PR China
c
Institute of Electron Device & Application, Hangzhou Dianzi University, Hangzhou, Zhejiang 310018, China

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

Article history: Graphenes are beneficial to electrons field emission due to its high aspect ratio, high carrier density, the
Received 15 December 2016 larger carrier mobility, excellent electrical and thermal conductivity, excellent mechanical strength and
Received in revised form 28 February 2017 chemical stability. In recent years, graphene or reduced oxide graphene field emitters have been success-
Accepted 7 March 2017
fully constructed by various methods such as chemical vapor deposition, chemical exfoliation, elec-
Available online 16 March 2017
trophoretic deposition, screen-printing and chemical synthesis methods. Graphene emitters are tried
to construct in distribution with some angles or vertical orientation with respect to the substrate surface.
Keywords:
The vertical alignment of graphene sheets or edges arrays can facilitate efficient electron emission from
Graphene
Reduced graphene oxide
the atomically thick sheets. Therefore they have even more a low turn-on and threshold-field electronic
Electron field emission field, high field enhancement factor, high current stability and high luminance. In this review, we shortly
survey and discuss recent research progress in graphene field emission properties with particular an
emphasis on their preparing method, characterization and applications in devices especially for vertical
graphene and single layer graphene, also including their challenges and future prospects.
Ó 2017 Elsevier B.V. All rights reserved.

1. Introduction
Graphene is a planar monolayer of carbon atoms arranged into a
two-dimensional (2D) honeycomb lattice structure [1]. It is one of
the allotropes for carbon element and it is the thinnest known
material in the universe. Since it was discovered by Novoselov
et al. [2], researching about graphene has quickly become an
immediate world-wide hot topic in scientific and engineering
fields [3–6]. Due to its unique properties (single-atom thick sheets
of sp2 bonded carbon atoms), graphene has high electrical conduc-
tivity, remarkably high carrier mobility in the room temperature
and chemical stability, it was recognized as a promising material
for highly conductive thin films in fabrication of the high-
performance field emission emitters, energy storage devices, pho-
todetectors, super capacitors and sensors [7–13]. Recent research
progress in graphene has evoked vastly interest in its application
as field emitters [14–16]. Graphene field emitters can be prepared
by the methods of micromechanical exfoliation, chemical vapor
deposition (CVD), electrochemical deposition, reduction from gra-
phene oxide etc. In comparison with carbon nanotubes (CNTs),
⇑ Corresponding authors at: College of Materials and Environmental Engineering,
Hangzhou Dianzi University, Hangzhou 310018, PR China (L. Chen).
E-mail addresses: chlf@hdu.edu.cn (L. Chen), wujun@hdu.edu.cn (J. Wu).
the possessing of rich edges may render graphene beneficial for
electrons tunneling through the surface potential barrier under a
low electronic field. The small size for resultant flakes can provide
numerous emission sites, and the high aspect ratio of a graphene
flake (lateral size to thickness ratio) facilitates field enhancement
[17–19]. In order to achieve excellent field emitters with a low
turn-on field and threshold field, high enhancement factor and
good emission stability, most of the studies are mainly focused
on constructing optimized graphene field emitters such as tailoring
the structural properties, density, work function, alignment and so
on [20–22].
To date, graphene field emitters have been successfully con-
structed by various methods and these emitters demonstrate
considerable promise for application in electron field emission
due to theirs outstanding properties [23–26], such as a high aspect
ratio, significantly improved conductivity, excellent mechanical
strength, chemical stability, reduced work function and good flex-
ibility [27–30]. Therefore they not only acquire improved contact
resistance between substrate and emitters for providing electri-
cally conductive channels for electron transportation and tunnel-
ing, but also obtain lowing work function, weakening the screen
effect of the neighboring emitters and increasing emission sites
[31–35]. So the graphene emitters have the low emission threshold
field, high emission current density, high brightness, long-term

http://dx.doi.org/10.1016/j.mseb.2017.03.007
0921-5107/Ó 2017 Elsevier B.V. All rights reserved.
 L. Chen et al. / Materials Science and Engineering B 220 (2017) 44–58
stability and reproducible performance. A comprehensive sum-
mery of graphene field emission is necessary for our better under-
standing and further prospects for the improved graphene based
field emission devices.
Electron field emission from two-dimensional nanostructures of
single layer graphene is worth of a further investigation because its
current field emission characteristic may be different from the
conventional Fowler-Nordheim (F-N) law [36–38]. The two-
dimensional geometrical effect for graphene, such as massless
Dirac fermion, may result in the new mechanism in electron field
emission [39–41]. Therefore graphene can offer us such a good
opportunity for the two-dimensional material research. A single-
layer graphene field emission is becoming an attractive topic in
recent years although its challenge for experimental measurement.
The high aspect ratio (thickness to lateral size ratio) and an observ-
ably enhanced local electric field from its sharp edges are beneficial
to electron field emission. A number of studies have already been
carried out on the field emission properties of varying dimensions
and orientations flakes. But they represent the average effects of a
large number of graphene. Those studies obscured the intrinsic
emission characteristics and mechanisms of an individual single
layer graphene or rGO sheet by collective behavior. For this reason,
it is necessary to find new mechanism in field emission from a
single-layer graphene or individual graphene by experimental
measurement [42,43]. A detailed analysis of electron emission
from individual freestanding single-layer graphene is also neces-
sary to understand the electronic structure at the graphene edge.
Therefore in this review, we shortly survey and discuss current
research activities about graphene field emission properties with
particular an emphasis on their fabricating method, characteriza-
tion, highlighting recent results and applications in devices
especially for vertical graphene and single layer graphene, also
including the challenges and future prospects.
2. Fabrication
Graphene is a two-dimensional (2D) single-atom thick sheet
which extends perfect honeycomb network. The 2D graphene
sheet is beneficial to electrons field emission for its high carrier
density, the larger carrier mobility, excellent electrical and thermal
conductivity and small electron mass values. Graphene also have
excellent mechanical properties with high breaking strength and
Young’s modulus [44,45]. Due to its nature of sharpness, graphene
can enlarge field enhancement factor. The high field enhancement
factor can easily extract electrons from surface of graphene under
considerable low bias. Studies in graphene and graphene oxide in
the past few decades laid a foundation in this field and it attracted
enormous attention for scientists working in constructing
graphene based field emission emitters [46–49]. Considerable
research interest has been concentrated on the design and fabrica-
tion of cold cathode electron field emitters (FEs) for applications in
vacuum microelectronic devices, such as X-ray sources and high
energy accelerators, and flat panel FE displays (FEDs) [50–53].
The technologies including exfoliation from graphite, elec-
trophoretic deposition (EPD), screen-printing, reducing graphene
oxide to reduced graphene and CVD were developing to fabricate
the graphene based field emission emitters in recent years
[54–59]. In this part, we will introduce some typical techniques
for graphene field emission emitter fabrication process.
2.1. Exfoliation
The simple and pristine fabricating process can be used for
exfoliation from graphite. Few layer graphene nanosheets field
emitters can be achieved utilizing liquid phase exfoliation from
45
graphite [60,61]. The commercial expandable graphite [54] flakes
were first heated in a microwave oven and then dispersed in etha-
nol by ultrasonication. By coating the graphene solution on a cop-
per substrate and drying at room temperature, the graphene field
emitter were easily obtained. Another example was prepared for
graphene emitters using convenience and inexpensive exfoliation
method [62]. By chemical process, commercially available carbon
cloth was used as starting material and graphene were exfoliated
from carbon fiber in carbon cloth. Fig. 1 illustrates the schematic
of graphene exfoliation mechanism from carbon cloth. Carbon
cloth woven by carbon fibers are shown in Fig. 1(a) and amplifying
diagram of carbon fibers composed of anisotropic graphite layers
and amorphous carbon is given in Fig. 1(b). The graphite layers
outside were terminated with functional groups after chemical
oxidation as provided in Fig. 1(c). The functional groups in oxidized
graphite layers were decomposed after heating and graphene were
exfoliated as shown in Fig. 1(d). The exfoliated graphene is not sep-
arated from carbon cloth, instead, they stay together with carbon
cloth and act as in situ emitters. The multistage structure can result
in the enhancement factor. The multistage field enhancement
factor and good contact between carbon cloth are beneficial to
electron field emission.
2.2. Electrophoretic deposition
EPD process is a fascinating technique for deposition graphene
and related materials [63–65]. It is an economical, convenient
and inexpensive process and can be used to fabricate graphene
emitters. EPD is a versatile processing technique, which can
achieve a homogeneous and controlled thickness of the obtained
film for preparation of thin film from suspension. EPD also has a
high deposition rate and throughput, no need of binders and sim-
plicity of scaling up [66,67]. The early works for preparing uniform
single-layer graphene field emitter were reported [68]. The film
has a high graphene density, uniform morphology and uniform
thickness. The film is randomly oriented, due to their good stiff-
ness, some of sheets are almost normal to the substrate. These
sharp edges can enlarge field enhancement factor and act as active
emission points. The relationship between surface topographic
structure and deposition time during EPD process was also studied
in detail in the same group [56]. The higher density of shorter
length and fewer thin layers graphene sheets can be obtained with
longer time deposition. The topographic structure of shorter-
length and thinner graphene sheets for long time deposition can
boost geometrical field enhancement factor, which thus can result
in better field emission properties.
2.3. Chemical vapor deposition
CVD method is a low cost, highly scalable route toward the fab-
rication of nanocarbon electronic devices. CVD consists of thermal
CVD [69], plasma enhanced chemical vapor deposition (PECVD)
[70] and hot-filament chemical vapor deposition (HFCVD)
[71,72]. Hydrocarbon such as CH4 is often chosen as carbon source.
Compared with thermal CVD, plasma deposition has many advan-
tages such as very short deposition time, a lower growth tempera-
ture and higher growth selectivity. The vertical graphene sheets
can be achieved using this method due to the plasma electric field
direction [48]. Using thermal CVD technique, the large area gra-
phene planar graphene and morphologically disordered graphene
were synthesized on copper foil [69]. The additional defects, edges,
and atomic scale ripples for morphologically disordered graphene
can result in more emission sites than that of planar graphene.
Employing the solid camphor as carbon source, using thermal
CVD method, an individual graphene flake can be also synthesized
[73]. The individual graphene sheet field emission can afford us
46 L. Chen et al. / Materials Science and Engineering B 220 (2017) 44–58

Fig. 1. Schematic of the graphene exfoliation on carbon cloth. (a) Carbon Cloth was woven by carbon fiber. (b) Amplifying diagram for carbon fibers consisted of anisotropic
graphite layers and amorphous carbon. (c) After chemical oxidation, the outside graphite layers were terminated by functional groups. (d) The graphene were exfoliated from
outside graphite layers after heating. Reproduced with permission from Ref. [62]. Copyright 2011, American Institute of Physics.

Fig. 2. Schematic illustration of the capacitively coupled radio frequency (rf) sputtering system used for the GNS growth. Reproduced with permission from Ref. [98].
Copyright 2013, Elsevier Ltd.

realizing the basic electron emission process from low dimension
materials such as graphene and carbon nanotube. Using a control-
lable capacitive coupled radio frequency (rf) sputtering deposition
system [98], without any catalyst, the vertically aligned ultrathin
graphene nanosheets can be synthesized as shown in Fig. 2. For
the vertical graphene sheets growth process, hydrogen was used
for glow discharge as well as for sputtering carbon coming from
a high-purity graphite target. Utilizing the mixture gas of methane
and hydrogen as precursor, the vertically aligned few-layer gra-
phene was synthesized in the absence of any metallic catalyst by
MPECVD [70]. The unique geometry of the PECVD synthesis
vertical orientation graphene can provide us investigation for the
field emission performance directly. After that the vertically
aligned few-layer graphene were constructed by many researchers
[74–76].
2.4. Printing
A sophisticated method which is widely used in large-scale
applications on different substrate is screen printing technology.
Due to its low manufacture cost, larger scale production, preferable
fabrication condition, the screen-printing method would be suit-
able for electronics technology [77–81]. This pioneer works for
preparing graphene field emitters were reported [82]. The gra-
phene power with organic binders was mixed and then the power
was screen-printed on electrical substrates as an emitter cathode.
At last, these samples were annealed to burn out the organic bin-
ders. For the printed samples, some graphene were wrapped with
each other and some were vertical to the surface of the substrate.
The protruding graphene sheets with sharp edges or tips could be
acted as vertical field emission sites. The unique structure of
printed graphene is beneficial to excellent emission properties.
The method of fabricating vertical graphene field emission cath-
odes based on a conventional screen-printing technique and then
following selective photoetching techniques was also developed
[83]. Fig. 3 presents the schematic for the vertical graphene cath-
odes fabrication process. Mixing graphene solution with negative
ultraviolet (UV) photoresist ink, the photoresist: graphene paste
was prepared and then the paste was screen-printed on the
cleaned indium tin oxide-coated (ITO) glass substrate as shown
 L. Chen et al. / Materials Science and Engineering B 220 (2017) 44–58 47

Fig. 3. Schematic of the fabrication procedures for screen-printing vertical graphene field emission cathodes. (a) Graphene solution with negative ultraviolet (UV) photoresist
ink screen-printed on the cleaned ITO coated glass substrate. (b) UV exposure conducted from backside. (c) The developing solution was sprayed on the top of paste. (d) The
developed vertical graphene sheets embedded in bottom of the past. Schematic for 3D graphene fin printing. (e) Graphene/PMMA stack transferred to structured PDMS
stamp. (f) Solvent bath dissolves the PMMA mediator. (g) Partial drying of the stamp releases the graphene. (h) Peeling of the stamp transfers the graphene to substrate
defining the fin-emitter geometry. Reproduced with permission from Ref. [83,84]. Copyright 2013, Elsevier Ltd and 2013, Wiley-VCH Verlag.

in Fig. 3(a). UV exposure was conducted from backside as exhibited
in Fig. 3(b) and the developing solution was sprayed on the top of
photoresist: graphene as shown in Fig. 3(c). Therefore the vertical
graphene sheets embedded in the bottom of past can be obtained
as provided in Fig. 3(d).
Using structured polydimethylsiloxane (PDMS) stamps, a
micro-transfer contact printing technique was developed [84]. This
technique can control graphene into vertically standing fins on
substrate. Fig. 3(e–h) shows the schematic of graphene fin printing
process. Fig. 3(e) presents that the graphene supported on poly
(methyl methacrylate) (PMMA) film is transferred onto a struc-
tured PDMS stamp. Fig. 3(f) provides solvent bath process to dis-
solve the PMMA layer. During this procedure, the graphene can
sink into the trenches of the PDMS stamp. Fig. 3(g) illustrates
regions of graphene fins adhered the trenches wall of the stamp.
Fig. 3(h) exhibits peeling of the stamp from any arbitrary substrate.
During this transferring process, point of the graphene is drawn,
and then graphene fins can be print into the substrate.
2.5. Other methods
The vertical alignment of graphene sheets or edges arrays
arranged along the direction of external electric field can guarantee
efficient electrons emission from the atomically thick sheets [85–
88]. Graphene are two-dimensional single layer graphite sheets
and they do not have high aspect ratio like carbon nanotubes
(CNTs). Although the high ratios of lateral size to thickness facili-
tates field enhancement, but most of the fabricated graphene
sheets always flatly lay on the substrate except for PECVD process,
which resulting in lack of sufficient field enhancement and the lim-
ited emission sites. These are challenges for fabricating of a low
turn-on field, low threshold field and reliability graphene field
emitter. Therefore graphene sheets are tried to construct in
distribution with some angles or vertical orientation with respect
to the substrate surface. Therefore, by effortless and inexpensive
fabrication ways, the vertically aligned graphene are favorable for
the next generation electron sources. Through filtration the highly

Fig. 4. Schematic diagrams of fabrication process for tubular structured RGO arrays. PCM filters with the pore size of 3 lm (b) and 5 lm(c), respectively. PCM etched in
chloroform (d). The ITO glass substrate picked up the floating RGO arrays (e). The controlled tube lengths and alignment of highly flexible RGO field emitters (f). Reproduced
with permission from Ref. [89]. Copyright 2012, The Royal Society of Chemistry.
48 L. Chen et al. / Materials Science and Engineering B 220 (2017) 44–58
Fig. 5. Scheme of the whole photolithography and etching processes in fabricating the proposed graphene field emission arrays (FEA) (a). An illustration of the designed
graphene FEA sample (b). Reproduced with permission from Ref. [18]. Copyright 2011, American Institute of Physics.
dispersed reduced graphene oxide (RGO) solution through a poly-
carbonate membrane (PCM), which possessing the pore size of
3 lm and 5 lm as shown in Fig. 4(b) and (c), aligned arrays of
tubular-structured RGO can be fabricated [89]. The schematic dia-
grams of fabrication process for the tubular structured RGO arrays
are shown in Fig. 4(d), (e) and (f). The PC membrane was first
exposed to UVO and then was selectively etched in chloroform as
shown in Fig. 4(d). At last, the floating RGO arrays were transferred
by direct contact with strong adhesion with indium tin oxide (ITO)-
coated glass as presented in Fig. 4(e). The controlled tube lengths
and alignment of highly flexible RGO field emitters were obtained
as provided in Fig. 4(f).Abundant sharp edges of vertical arrays of
tubular-structured graphene can guarantee excellent field emis-
sion due to sufficient field enhancement factor.
Employing an easy method of photolithography and wet etch-
ing process, the well-aligned graphene field emission arrays were
developed on copper foils [18]. Fig. 5. presented the whole fabrica-
tion procedure. The obtained graphene sheets on copper were pre-
pared by CVD process as shown in (1). 1 lm thick positive resist
was spin coating on graphene surface as shown in (2) step. In step
(3), after baking on a hotplate (120 °C for 2 min) and then masking,
and then positive resist was exposed in a proximity printer. Step
(4) was exposed parts of pattern the graphene/Cu after cleaning
using NaOH solution. In 20 sccm air at 90 W for 3 min, plasma etch
was used to move the exposed graphene as exhibited in (5) step. In
step (6), wet etching was applied to clean the exposed copper sur-
face in FeCl3 solution for 15 min. Finally, in step (7), the masking
resist was removed in acetone to obtain the desired graphene
emission array on copper. The high uniform micro sized graphene
pattern in the array elements was achieved by the low cost top-
down parallel method. The vertical graphene edges or tips on a
well-aligned high-ordered pattern can contribute to the high emis-
sion current density. Fig. 5(b) is an illustration of the designed gra-
phene field emission arrays sample.
3. Characterization
The morphologies of the prepared graphene field emitters are
often characterized by scanning electron microscope (SEM) or
transmission electron microscopy (TEM) [90,47,91–94]. The image
and the thickness of graphene are also investigated by atomic force
microscope (AFM). High-resolution TEM is often used to analyze
the structure, thickness and number of layers [97]. The structure,
electronic properties and elemental analysis of graphene are fre-
quently utilized to characterize by Raman spectroscopy, X-ray
photoelectron spectroscopy (XPS) and X-ray diffraction (XRD)
[98,99]. In this part, we will discuss the difference characterization
methods for difference fabrication arts in the relevant representa-
tive examples in detail.
3.1. 1Microscopic techniques
For graphene field emitter morphology, composition and crys-
tallographic information, SEM and TEM are extensive used as char-
acterization tools. For example, Fig. 6(a) shows the magnified side-
view SEM image of PECVD growth graphene, which possessing a
‘petal-like’ morphology and highly dense. The orientations of the
graphene sheets are approximately vertical aligned to the sub-
strate [124]. The vertical orientation graphene sheets can locally
enlarge the electric field and promise electrons to tunnel through
the sharp sheets easily at very low electric fields. Fig. 6(b) and (c)
show SEM and TEM images exhibiting the sheets about several
nanometers in thickness and about 200 nm in height. From Fig. 6
(c) of HRTEM image, we can see the space between the proximate
graphene layers is about 0.34 nm, as we know it is a graphitized
structure. AFM is also applied to character the image and the thick-
ness of graphene. AFM image of graphene sheets prepared from
natural graphite using chemically reduced graphene oxide is
shown in Fig. 6(d) [83]. The cross sectional analysis of the selected
region between the two arrows is shown in inset. From Fig. 6 (d),
we can see the thickness of the graphene sheets layer is about
3 nm.
3.2. Raman spectroscopy
The structure and electronic properties of graphene are often
investigated by Raman spectroscopy. Three prominent features in
the spectra, located at about 1350 cm
1 (D band), 1580 cm
1
(G band), and 2700 cm
1 (2D band) can be exhibited in graphene
spectroscopy. The D peak at about 1350 cm
1 represents the disor-
dered carbon content originating from backscattering of phonon by
edge or defect. While, the G peak at about 1580 cm
1 represents
the graphite content derived from the doubly degenerate phonon
mode (E2g symmetry). The 2D-bandlocated at 2700 cm
1 origi-
nates from a second order process involving two phonons near
the K point. The K point is the p⁄ and p bands touched at the cone
corners of the hexagonal Brillouin zone and it is also called Dirac
point [100,101]. The ratio of ID/IG can reflect the crystalline quality
of graphene and the ratio of the I2D/IG also reflect the graphene
quality. A typical Raman spectrum of as-grown vertically standing
graphene by CVD method [102] is shown in Fig. 7(a). There are
three major features in the spectra, located at 1350 cm
1 (high-
intensity D band), 1582 cm
1 (G band), and 2700 cm
1 (2D band).
The ratio of the intensities of the G and 2D bands is nearly 1,
 L. Chen et al. / Materials Science and Engineering B 220 (2017) 44–58 49

Fig. 6. (a) The side-view SEM image, (b) TEM and (c) HRTEM image for as-grown few layer graphene sheets (FLGSs). (d) AFM image of dispersive graphene sheets on silicon
substrate. Reproduced with permission from Ref. [124,83]. Copyright 2010 IOP Publishing Ltd and Copyright 2013, Elsevier Ltd.

showing multi-layer type graphene features. A single Lorentz
shape fitting of the 2D band is shown in inset of Fig. 6(a). The
Raman spectrum of the RGO [89] is presented in Fig. 7(b). The
2D peak (2685 cm
1), which possessing symmetric line shapes
and no shoulder peaks illustrate the existence of a single-layered
graphene in the RGO. The intensity ratio of ID/IG was 1.3. From
Fig. 7(a) and (b), we can see graphene prepared by CVD has less
defects than that of chemical reduction method. Therefore the
quality and the number of the graphene layers are often character-
ized using Raman spectroscopy as no destructive tools by many
researchers.
3.3. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction
(XRD)
The information for elemental compositions of graphene emit-
ter surface or functionalized graphene can be analyzed using XPS
technique so as to better understand their surface chemical states
that are directly correlated to their electrical properties. Graphene
emitters by CVD as shown in Fig. 8(a) exhibited strong signals cor-
responding to C (1 s) arising from sp2 carbon at 284.8 eV, while a
small O 1 s peak at 532.7 eV and a weak O KLL Auger band between
970-980 eV [102]. From the XPS analyzing, it can be seen the gra-
phene fabricated by CVD possessing high quality except only some
oxygen adsorbates on the surface. The physical and chemical
adsorption of oxygen resulted in oxygen adsorbates in the edge
defects for the sample exposing to ambient conditions at room
temperature. As shown in inset of Fig. 8(a), due to CAO, C@O, the
tail between 286 eV and 290 eV is appeared. XRD can be also one
tool for determination the properties of graphene emitter. Gra-
phene can be reduced from graphite oxide, as shown in Fig. 8(b),
XRD pattern shows GO with a wide peak at 10° due to existence
of oxide functionalized group. It indicated damage of lattice of
graphite [95]. The peak concentrated at 10° was nearly fully
removed after reduced, which illuminating formation of single
layer or several layers graphene as shown in Fig. 8 (b). The reduced
graphene oxide presented a broad peak located at 26.5°, which
deriving from the carbon (002) plane of the hexagonal structure.

Fig. 7. Raman spectrum of vertically standing graphene by CVD (a) and (b) RGO. Reproduced with permission from Ref. [102,89]. Copyright 2013, Wiley-VCH Verlag and
2012, the Royal Society of Chemistry.
50 L. Chen et al. / Materials Science and Engineering B 220 (2017) 44–58
Fig. 8. (a) XPS of the graphene sample, the inset showing the C1 s spectrum. (b) XRD images of graphite, GO and reduce graphene oxide sheet produced by microwave (MW)
and hydrazine (HR). Reproduced with permission from Ref. [102,95]. Copyright 2013, Wiley-VCH Verlag and 2011, Elsevier Ltd.
4. Field emission
4.1. F-N theory
Field-emission can be described as a quantum tunneling pro-
cess in which electrons escape from cathode material to an anode
through a vacuum barrier under applying the external electrical
field. The Fowler–Nordheim (F-N) law describing electron field
emission originates from early research about flat metallic sur-
faces, but now it is extensively used in carbon or other materials
based on electron emission [103]. The field emission properties
of graphene can be also discussed by using F-N equation. According
to the theory, the relationship of field emission current density J
with the applied electric field E is analyzed by
 
ðbEÞ2 /3=2
J ¼ ga exp
b
/ bE
where J is the current density, a and b are constants,
a = 1.54  10
6 A eV V
2 and b = 6.83  103 eV
3/2 V
1 lm; / is
the work function, g is a factor describing the geometrical efficiency
of emitters, b is the field enhancement factor, and E is the macro-
scopic electrical field in V/lm, E is usually taken as E = V/d, where
V is the applied potential, d is the distance between cathode and
anode. It can be obtained a plot through plotting ln (J/E2) versus
E
1. If the plot exhibits a linear property, we can conclude that
the observed current is essentially electron field emission from tun-
neling barrier. As one can see from Eq. (1), field emission perfor-
mances are related to two important factors of work function and
field enhancement factor. With increasing the b or deceasing the
/, the field emission current density can be increased. Generally,
the b is the ratio of local electric field to macroscopic electric field.
As we know it is approximately proportional to the aspect ratio of
the emitters. According to slope of the F-N plot (kFN), the b can be
calculated using the following equation [104,105].
b ¼ b/3=2 =kFN
The turn-on field (Eto), threshold field (Eth), emission stability
and luminescent intensity are another parameters for evaluating
the field emission performances. The low Eto and Eth, the high b
and emission current density, the uniform and high image and out-
standing emission stability are important for a better field emitter.
4.2. Multilayer graphene field emission
Graphenes are two-dimensional single layer graphite sheets
and they do not have the sharp tips like CNTs. But the wrinkled
edges or tips of graphene can act as field emission sites. Graphene
sheets are often tried to construct with some angles distribution to
the substrate. Graphene field emission behaviors are relevant to
different fabricating methods. Even using the same preparing
method, difference experiment conditions may result in the differ-
ence field emission properties. As we know that the obtained gra-
phene sheets can easy tend to form irreversible agglomerates or
restack through Van der Waals forces interaction. Therefore, gener-
ally, the observed field emission comes from more than three lay-
ers of graphene flakes, which representing the collective effects of
a number of graphene properties. In this section, we will discuss
the multilayer graphene field emission performance including dif-
ference fabrication processes, and we will emphasize the vertical
graphene field emission performance.
The fabricated graphene sheets flatly lay on the substrate which
results in lack of sufficient field enhancement. Therefore graphene
emitters are tried to construct in random distribution with some
ð1Þ
angles or vertical orientation with respect to the substrate surface.
In the previous work for EPD graphene emitters, with some sheets
being normal to the substrate, the graphene displayed turn-on
fields of 2.3 (10 lA/cm2), the threshold fields of 5.2 (10 mA/cm2)
and field enhancement factor of 3700 [68]. In the early work of liq-
uid phrase exfoliation graphene emitters with some graphene
sheets protruding from the surface, the graphene emitters have
even a low turn-on field of 1.7 V/lm (10 lA/cm2) and the thresh-
old field of 3.7 V/lm (1 mA/cm2) [54]. The larger lateral size to
thickness ratio resulted in the larger enhancement factor of 7300.
The following results can further verify that the vertical orientation
graphene can give larger contribution for graphene field emission.
The reduced graphene oxide emitters were fabricated on polymer
film by coating. Electron field emission performances in both par-
allel and perpendicular configurations were studied [96]. Due to
difference orientation of the graphene on the substrate, in perpen-
dicular configuration, a low turn-on field of 0.6 V/lm and a very
high emission current density of a 200 mA/cm2 at 1.65 V/lm were
achieved. In parallel configuration, due to most of graphene lay
ð2Þ flatly on the substrate, a high turn-on field of 6 V/lm and a high
current density of a 20 lA/cm2 at 10.5 V/lm are only got. So the
field emission capabilities were restricted by the orientation distri-
bution of the graphene sheets.
The screen-printing technique can be used to construct larger
scale graphene field emission emitter. The screen-printed gra-
phene emitters with some stiffness edges vertical to the substrate
surface can contribute to good field emission. Screen-printed gra-
phene emitters with some vertical graphene sheets have a low
turn-on electric field of 1.5 V/lm (1 lA/cm2), a low threshold field
of 3.5 V/lm (1 mA/cm2) and the enhancement factor b of 4539, as
showing in Fig. 9(a) [82]. Field emission image of screen-printed
graphene emitters is shown in the inset of Fig. 9(a). The F-N plot
 L. Chen et al. / Materials Science and Engineering B 220 (2017) 44–58 51

as shown in Fig. 9(b) has a good linear character. As shown in the
inset of Fig. 9(b), in order to evaluate the stability of the field-
emission current of screen-printed graphene films, emission cur-
rent density around 1 mA/cm2 for 180 min was measured. The
fluctuation of the emitting current was within 10%, which showing
good stability. Ideal field emission model of screen-printed gra-
phene ‘emitting group’ is shown in Fig. 9(c). The emitting groups
with sharp edges are vertical to the substrate and probably respon-
sible for their good emission properties.
By screen-printing process, if the graphene have most vertical
graphene sheets, they can exhibit outstanding emission perfor-
mance. Another screen-printing technique of preparing most of
vertical graphene field emission cathodes are also developed
[83]. The vertical screen-printing graphene emitter field emission
performance is better. The schematic of screen-printed vertical
graphene cathode with parallel emitting areas is shown in Fig. 9
(d). The right of bottom and top are the optical image of the
screen-printed vertical graphene cathode and the corresponding
luminescence pattern, respectively. The uniform emission pattern
can be achieved because electrons emitted from the homogeneous
graphene edges. The J-E curve obtained from the screen-printed
vertical graphene cathode is shown in Fig. 9(e). The turn-on field
and the threshold field for vertical-graphene-based field emission
device are 1.56 V/lm (10 lA/cm2) and 5.12 V/lm (10 mA/cm2),
respectively. The vertical-graphene devices possess the high cur-
rent density of 40 mA/cm2 at 6.0 V/lm, and good emission stabil-
ity. The field emission properties are comparable or even better
than those of graphene emitters fabricated by CVD or other
methods.
The vertical alignment of graphene sheets, due to high local
field enhancement, can guarantee electrons to easily tunnel into
vacuum at low electric fields. In order to improve graphene field
emission properties, many methods are tried to construct verti-
cally standing graphene on substrates. The graphene emitters fab-
ricated by CVD method with almost all of vertical sheets can
possess excellent field emission properties. Vertical orientation of
a few-layer graphene was synthesized in the absence of any metal-
lic catalyst employing MPE-CVD [70]. The turn-on electric field as
low as 1 V/lm (10 lm/cm2) and the field amplification factors up
to several thousands (7500) for the vertical orientation were
obtained. The authors observed a clear dependence of the few-
layer graphene field emission behavior on the synthesis parame-
ters and difference substrates. Samples grown on titanium with a
large H2/CH4 gas ratio show enhanced field emission of a lower
turn-on field values and higher amplification factors.
In the past few years, the flexible devices have attracted much
attention in vacuum micro-electron devices such as field emission
display [106–108]. The application of graphene in flexible electron-
ics could open up breathtaking applications in foldable devices in
the future [109,110]. For flexible graphene based electron devices
construction, the combination of graphene and organic semicon-
ductors or inorganic nanomaterials is often used as the active
materials with graphene. The high-performance flexible patterned
RGO field emitters with vertically aligned tip structures are suc-
cessful fabricated [51]. The vertically aligned patterned RGO arrays
were achieved on SWCNT-coated polyethylene terephthalate (PET)
substrate. The electrical conductivity of the RGO array film did not
change significantly even under severe bending conditions. The
flexible RGO arrays cathodes and J-E curves for difference bending
angle are presented in Fig. 10. Fig. 10(a) provides an optical pho-
tograph of flexible cathode array with 2 cm  2 cm in size. Fig. 10
(b) exhibits the high magnified SEM image of the RGO arrays,

Fig. 9. (a) The J-E plot of screen-printed graphene films with a vivid emitting picture (black) and graphite films (red) and field emission image of screen-printed graphene
emitters showing in the inset. (b) The F-N curve of graphene cathode reveals a field enhancement factor of 4539 and the inset showing the emission stability of screen-
printed graphene films. (c) Ideal model of screen-printed graphene ‘emitting group’. (d) Schematic of field emission device bases on screen-printing vertical graphene
cathodes. The bottom right is the optical image of the screen-printed vertical graphene cathodes, and the top right is the corresponding luminescence pattern. The scale bar is
1 cm. (e) J-E curve of the screen-printing vertical graphene emitters, and the inset showing the F-N plot. Reproduced with permission from Ref. [82] and [83]. Copyright 2009,
IOP Publishing Ltd and Copyright 2013, Elsevier Ltd. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
52 L. Chen et al. / Materials Science and Engineering B 220 (2017) 44–58

excellent field emission for flexible emitter. In the inset of Fig. 10

(c) show field emission image of the flexible RGO array at bending
angle of 30° and at applied electric field of 2.78V/lm. Bright and
uniform electron emission image were resulted from the high crys-
tallinity, high chemical and mechanical strength of vertical arrays
with sharp tips respect to the substrate. Table 1 presents field
emission parameters of multilayer graphene emitters fabricated
by different methods in recent years.

4.3. Single layer graphene field emission

4.3.1. The monolayer graphene

Fig. 10. (a) Optical photographs of flexible RGO arrays fabricated on a SWCNT-
deposited PET film. (a) SEM image of high magnification of bent RGO arrays. (c) J–E
characteristics of patterned RGO arrays as a function of the bending angle. The
emission pattern from a flexible RGO arrays 2 cm  2 cm in size, for a bending angle
of 30°. Reproduced with permission from Ref. [51]. Copyright 2013, Wiley VCH.
which showing the vertical alignment tips relative to the substrate.
Fig. 10(c) shows the J–E plots for the flexible emitter with differ-
ence the bending angles. From the J-E plots, we can see that the
current density almost did not change with the bending angle.
The numerous vertical RGO nanosheets and good interfacial
contact between the RGO arrays and the substrate resulted in
For monolayer graphene field experiment measurement, it
should be performed in a SEM chamber. Both of Xiao [112] et al.
and Santandrea [111] et al. reported field emission from single
layer graphene. Fig. 11(a) shows photograph of a SEM chamber
with equipped with a nanomanipulator for field emission experi-
ment. Xiao et al. prepared a single graphene sheet using mechani-
cal cleavage method. The nanomanipulator fixed with a cleaned
tungsten tip was used as the anode probe. In order to make the
single-layer graphene visible under optical microscope, they
placed the single-layer graphene on silicon substrate covered with
a SiO2. Using e-beam lithography, sputtering deposition and lift-off
process, gold electrodes were deposited on the two ends of a
single-layer graphene. Field emission measurements were carried
out on difference places of the graphene single layer which marked
as A-E as shown in Fig. 10(b). From Fig. 10(b), we can see point A
and point E are at the edge lying flatly on the substrate and at
the center of the graphene single layer, respectively. Points B-D
is at the edge above the substrate. No field emission currents were
observed in points A and E only negligible currents with a noise
level of about 2pA. However, with fields even below 800 MV/m,
field emission currents above 100pA could be observed from points
B-D. These results illuminated that the edge of a single-layer
graphene is beneficial to electron field electron. More specific
equations for high- and low-field cases were obtained as
ln(I/Ea)  1/Eb, where (a, b) = (3/2, 1) for the high-field regime
and (a, b) = (3, 2) for the low-field regime. The F-N plots exhibit
no linearity properties with an up-bending feature. It reveals that

Table 1
The turn-on fields (TOF) (V mm
1), the threshold fields (TF) (V mm
1) and field enhancement factor (FEF) for multilayer graphene or reduced graphene oxide (GP or RGO) emitters
fabricated by different methods in recent years.

Samples TOF TF FEF (b) Ref. Year

Exfoliation GP 1.7(10lA/cm2) 3.7(1 mA/cm2) 7300 [54] 2010
GP exfoliated from 0.4(10lA/cm2) 0.7(1 mA/cm2) 1.3  104 [62] 2012
Carbon cloth
Electrophoretic 2.3(10lA/cm2) 5.2(10 mA/cm2) 3700 [68] 2009
deposition
Screen-printing 1.5(1lA/cm ) 2
3.5(1 mA/cm ) 2
4539 [82] 2009
Microwave plasma CVD 1.3(10lA/cm2) 3.0 (1 mA/cm2) 1.1  104 [102] 2013
Microwave plasma 1(10lA/cm2) 2.1 (1 mA/cm2) 7500 [70] 2008
Enhanced CVD
Radio frequency sputtering 2.522(10lA/cm2) 3.401 (1 mA/cm2) 1781 [98] 2013
Screen-printing 1.56(10lA/cm2) 5.12 (10 mA/cm2) 3892 [83] 2013
Vertical-graphene
Reduced oxide GP 0.6 (3 mA/cm2) 1.65 (200 mA/cm2) 5818 [96] 2013
Vacuum filtered graphene 0.76(10lA/cm2) 1.35 (1 mA/cm2) 3  104 [95] 2011
Films reduced by microwave
Self-Organized reduced 2.04(10lA/cm2) 3.09 (1 mA/cm2) 3200 [51] 2013
Oxide GP
A route assisted vapor 1.81(10lA/cm2) 2(1 mA/cm2) 17140 [97] 2011
Solid process GP strips
Tubular-structured RGO 1.89(10lA/cm2) 3.51(1 mA/cm2) 4624 [89] 2012
Floral-clustered few-layer
GP nanosheet array 2.6(10lA/cm ) 2
5.8(1 mA/cm ) 2
3788 [23] 2012
 L. Chen et al. / Materials Science and Engineering B 220 (2017) 44–58 53

Fig. 11. (a) Photograph of the SEM chamber. (b) A 3D schematic illustration shows the relative position among anode probe, graphene, test points, and substrate. Reproduced
with permission from Ref. [111,112]. Copyright 2011, American Institute of Physics and 2010, American Chemical Society.

during field emission process single-layer graphene can undergo a
low-to high field regime transition. The related physical mecha-
nism responsible for the new field electron emission characteriza-
tion was also discussed by theoretical analysis. These findings
could provide a deeper insight way to understand field emissions
from a two-dimension system.
It is clearly that the sharp edges of graphene can dramatically
enlarge local electric field and enhance monolayer graphene field
emission properties. Almost no field emission currents were
observed in flat part reported by Xiao etc. Santandrea [111] and
coworkers investigated and characterized a single-layer graphene
field emission from the inner, flat part of graphene flake. This result
was different from the result of Xiao’ resports [112]. Using
mechanical exfoliation, a single-layer graphene sheet was prepared
and transferred on SiO2 layer covered on p-type Si substrate. In the
SEM chamber, there were two nanomanipulators which each has
tungsten tip used for field emission measurements. One tip was
in contact with graphene used as the cathode and the second
was used as the anode at a varying distance from it. Scheme of
the measurement setup is shown in Fig. 12(a). Field emission
experiments were performed in vacuum chamber at a pressure
of 10
6 Torr and room temperature. During field emission

Fig. 12. (a) Schematic view of the experimental setup using an external source measurement units interconnected to nanomanipulators in SEM chamber in Fig. 11(a). (b) I–V
curves measured for increasing graphene anode distance; (c) linear FN plot for FE characteristic sweep 4. Inset presenting SEM image of single layer graphene. F-N plot in the
ln(I/E3)  1/E2 coordinate (d). Reproduced with permission from Ref. [111,112]. Copyright 2011, American Institute of Physics and 2010, American Chemical Society.
54 L. Chen et al. / Materials Science and Engineering B 220 (2017) 44–58

measurement, the cathode tip was in contact with the graphene
flake and the anode was at a given distance from the flake.
Fig. 12(b) shows typical I-V measurements. Sweep 1 and sweep 2
curves were conditions in which both probes were contacted with
graphene flake. For sweep 3, when the anode was detached from
graphene, it exhibited a change behavior of field emission current
starting around 55 V. Due to effect of electrostatic attraction, the
graphene-anode contact was soon re-established. Sweep 4 was
field emission current above 100 V for the entire voltage sweeping
range up to 175 V. The field emission current in sweep 4 follows
the standard F-N model, as shown in Fig. 12(c). Inset of Fig. 12(c)
presents SEM image of single layer graphene sheet. This is differ-
ence from report of Xiao et al. that the plots exhibit no linearity
properties with an up-bending feature as shown in Fig. 12(d).
4.3.2. The single layer of reduced graphene oxide
The reduced graphene oxide (RGO) sheets are reduced from the
graphene oxide and a small fraction of the sheet edges may be
decorated with residual C-O-C cyclic ether group. How about the
C-O-C ether groups at the RGO edge influence the field emission
properties? How about the relationship between the electron
beams emitted from difference sites. The individual RGO sheet
was prepared from suspensions of chemically derived graphene
oxide (GO) using a simple and reproducible methodology [113].
The single-layer graphene was mounted on copper sheet for the
field emission experiments test. A direct bias voltage was applied
to the RGO cathode and anode plate. The threshold field required
to drive current of 1 nA was not more than 0.1 V/lm for the
atomically thin RGO sheets. A decrease in work function of the cyc-
lic CAOAC ether group edge and in combination with geometric
field enhancement resulted in good field electron emission. With
the applied voltage increase, the field emission current increased
exponentially, it reveals that the electron field emission follow
the F-N law. Both of the large enhancement factor of 3538 and
lower local work function at the edge resulted in the low threshold
field. Field emission stabilities for atomically RGO sheets exhibited
high stability with no drastic change. As shown in Fig. 13(a), field
emission microscopy presents emission patterns consisting of
alternating bright and dark fringe bands from emission sites at
anode voltage of above 2 kV. Fig. 13(b) gives the schematic model
of the field emission from the RGO edge. As we know, electron can
be easily escaped from low work function CAOAC ether chain
regions as shown by the red rectangles. The emitted electron
beams from the near two sites would have similar phase character-
istics due to the similar electronic structures. Interference from
sufficiently close electron beams can be happened because the
emission sites were separated by a few nanometers. Field emission
microscopy simulations and field ion microscopy results suggested
that the emitted electron beams interfere with each other and
produce fringe patterns. These results exhibit that atomically thin
RGO edges can be used as the high quality linear sources for high
density electron beams. In addition, the coherent electron beams
of the RGO may open up new applications such as vacuum elec-
tronics and optics devices.
Table 2 presents field emission parameters of different emitters
fabricated by different methods in recent years. From the table
Ⅰand Ⅱ, we can see that graphene has a low turn-on field, threshold
and high field enhancement factor. Therefore graphene has

Fig. 13. (a) Field emission microscopy patterns as a function of applied voltage. Fringe patterns were observed at anode voltage of 2 kV. The arrows in (iii) indicate the major
bands in the FEM pattern. (iv) Intensity profile of (iii) across the fringe region. The arrows indicate the position of minor bands. (v) Simulated FEM patterns for the case of
three aligned emission sites. (b) Schematic model of the field emission from the RGO edge. Field emission occurs from low work function C-O-C functionalized regions
containing at least 7 oxygen atoms, as indicated by the red rectangles. The prevalent nonoxygenated edges are higher work function. Interference from sufficiently close
electron beams is also depicted. Reproduced with permission from Ref. [113]. Copyright 2011, American Chemical Society.
 L. Chen et al. / Materials Science and Engineering B 220 (2017) 44–58 55

Table 2

1
1
The turn-on fields (V mm ), the threshold fields (V mm ) and field enhancement factor for different field emitters fabricated by different methods in recent years.

Field emitters TOF TF FEF (b) Ref. Year

Carbon nanotube arrays 0.85(0.1 lA/cm ) 2
1.67(1 mA/cm ) 2
3517 [114] 2008
Carbon nanowalls 4.7(0.1 mA/cm2) 6(1 mA/cm2) 1399 [115] 2015
ZnO nansheets arrays 2.4(0.1 lA/cm2) 6.4(50.1 lA/cm2) 5812 [116] 2014
Si nanowires 2(10 lA/cm2) 3.4(1 mA/cm2) — [117] 2006
WS2 nanotube — 1.5(1 lA/cm2) 3526 [118] 2014
Nano-diamond films 2.2(1 lA/cm2) 6.4(0.72 mA/cm2) — [119] 2003
GaN nanowires 9.1 (0.1 mA/cm2) — 730 [120] 2011
TiO2 nanotube arrays 2.8(1 lA/cm2) 8.0(0.15 mA/cm2) 5580 [121] 2006

advantages in field emission performances compared to other field
emitters.
5. Challenge and perspective
Field emission from graphene is still a challenge because the
fabrication methods such as micromechanical exfoliation, screen-
printing and electrochemical deposition etc, can result in sheets
laterally laid flat on the substrate which is disadvantageous for
electron tunneling from the surface barrier. Liquid-phase exfolia-
tion can be utilized to achieve bulk graphene sheets field emitters,
but the shapes are not uniform with a random distribution whilst
requiring transfer techniques, which limiting practical field emis-
sion properties. The screen-printing method is a simple technology
for the preparation of large-scale graphene field emission cathodes,
but organic binders mixed with graphene introduced during the
fabrication process can result in high resistance of emitter and high
contact resistance. Vertical aligned graphene can be synthesized by
CVD methods [122,123], but the relatively high growing tempera-
ture, complex process, time-consuming and high cost have become
drawbacks for its use in large-scale field emission devices, which
limiting the use of the low temperature substrate such as ITO
etc. Some time, post treatment is also needed to optimize the field
emission performances of CVD grown graphene such as plasma
treatment [124,57,125,14]. At the same time, to improve the adhe-
sion between graphene based field emitters and substrate is also
important for their practical applications. A weak interfacial con-
tact will result in high interface resistance and poor electron trans-
fer processes between emitters and substrates. Therefore, interface
engineering is often being considered as a scientific fabricating
process to improve the field emission performance of graphene
emitters [126–129].
The remarkable electrical, mechanical, and chemical properties
of graphene make it charming material for transparent electrodes
especially in next-generation display technology. To date, all kinds
of methods have been developed for design and fabrication of
graphene for their potential application in field emission. However,
the low-cost, large-area, high quality and yield of the products are
still far away from the need of practical field emission application.
The fabrication of graphene with optimized sizes, controllable
shapes, high conductivity, remarkable stability and preferable
synergistic effect is yet a challenge in expanding the fundamental
properties and potential applications. One of the most promising
directions is to develop excellent field emission performance
graphene emitters with low-costs and suitable for industrial-
scale production which can meet the demands of our daily life.

Fig. 14. (a) Cross-section schematic of the display. The electrodes forming the triode structure are the Ag gate, the Ag top cathode and the phosphor/ITO/glass anode which
are separated from the glass gate-cathode substrate by 3 mm ceramic spacers. (b) A scanning electron micrograph (false colored) of a complete graphene edge emission
structure showing the gate and cathode (cath.) electrodes, as well as the ZnO tetrapod electron scatterers (Scale bar: 200 lm). (c) A scanning electron micrograph (false
colored) of a single ZnO tetrapod and graphene edge (Scale bar: 5 lm). (d) A cross-section scanning electron micrograph (false colored) of the cathode, as indicated by the
dashed line in (c), showing the graphene edge emitter supported by an array of CNT bundles (Scale bar: 1 lm). Note that the cross section of the gate electrode has an
equivalent structure. (e) Simulated potential distribution (color bar, V) and electron trajectories (red curves) at the graphene edge. (f) Optical micrographs of a prototype
21 cm diagonal graphene electron emission display. Inset: Optical micrograph of a 23 pixel  11 pixel section of a fabricated display panel. Reproduced with permission from
Ref. [130]. Copyright 2013, Elsevier Ltd. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
56 L. Chen et al. / Materials Science and Engineering B 220 (2017) 44–58
Although some inspiring results have been achieved in previous
studies, such as low turn on fields and high field-enhancement
factors, but some problems limited their wide application are
encountered, such as the deterioration of field emission
properties due to the polluting or burning away emitter tips, the
uncontrollable emission sites and short life time. From a techno-
logical point of view, an ultra high and stable emission current
density, and reproducible performance are highly necessary for
commercial requirement. In order to meet these demands,
alignment uniformity, tailoring the density and shape of the emit-
ters and optimizing the intrinsic properties such as work function
and conductivity can remarkably improve the field emission
performance.
Although many difficulties are faced in the graphene based field
emitter fabrication, the research about graphene is going on and
the graphene based field emission display has been already suc-
cessful developed. The novel fully sealed 320  240 pixel of
21 cm diagonal graphene-based field emission display panel
capable of real-time video was fabricated [130]. Cross-section
schematic of the display is presented in Fig. 14(a). Employing a
screen-printing process, graphene supported on vertically aligned
CNT and the integrated ZnO tetrapod were fabricated as edge
emitters and electron scatters, respectively. A typical schematic
diagram of the whole graphene edge emission structure is
exhibited in Fig. 14(b). The SEM image of single ZnO tetrapod
and graphene edge is shown in Fig. 14(c). A cross-section SEM of
the cathode showing the graphene edge emitters supported by
an array of CNT bundles is provided in Fig. 14(d). Fig. 14(e) illus-
trates the distribution of the electric potential and electron trajec-
tories at graphene edge. Simulated edge electron trajectories
confirmed the experimental field emission properties. Fig. 14(f)
shows excellent uniform optical images of the monochromatic
21 cm diagonal graphene electron emission display panel. A 23
pixel  11 pixel optical micrograph section of the fabricated
display panel is shown in the inset of Fig. 14(f). The new display
panels show low driving voltages (<60 V) with high emission
efficiency (>90%), almost hysteresis free (<0.2%), extremely stable
lifetimes (<3% variation over 10 h) and rapid temporal responses
characteristics (<1 ms).
6. Conclusions
In this article, we have briefly surveyed and reviewed the recent
research progress in the region of graphene field emission proper-
ties. We focused on the design and fabrication process, character-
ization and field emission properties with emphasis of vertical
orientation and single layer graphene. The fabrication of graphene
with optimized sizes, controllable shapes, high conductivity,
remarkable stability and preferable synergistic effect is yet a chal-
lenge in expanding the fundamental properties and a potential
application, although some exciting results have been achieved
in previous researches. The fabrication and application of graphene
field emitters are still a challenge as following.
(1) The present fabrication methods often result in graphene
sheets laterally laid flat on the substrate, which are disad-
vantageous for electron tunneling from the surface barrier.
The vertical alignment of graphene sheets arrays arranged
along the direction of external electric field can guarantee
superior efficient electrons emission performance.
(2) The large-scale and low-cost fabrication of the graphene is
another critical issue for their industrial-scale production.
The complex process, small-scale, time-consuming and the
high cost have become larger drawbacks for its use in
large-scale field emission devices especially in commercial
market competition.
(3) At the same time, interface engineering is also an important
problem for optimization the field emission performance.
The good interface contact is beneficial to electron tunneling
and transportation. Therefore interface engineering is often
being considered as a scientific fabricating process for high
performance of graphene field emission emitters.
For vertical alignment of graphene sheets arrays emitters, regu-
lar geometry graphene arrays can be prepared such as by low tem-
perature CVD technique. For the large-scale and low-cost
fabrication of the graphene emitters, the prepared methods and
the related constructed approaches should be improved and devel-
oped combining with other advanced techniques. For interface
engineering, stronger bonds between substrate and graphene
should be built during fabrication process. So we believe that, with
research going on, graphene field emission properties can be
improved greatly in the future research as we expect.
This review not only provides an updated progress on the
design and construction of all kinds of graphene field emitters,
but also demonstrates their important applications in field emis-
sion. The discussion on the fabrication process, emitter character-
ization and field emission properties can offer fundamental
insights into the understanding and design of graphene emitters
for further optimization and improvements. The review can broach
the subjects and inspire readers in field of nano-materials such as
graphene based emitters.
Acknowledgments
The authors would like to appreciate the financial supports of
the State Key Laboratory of Silicon Materials Visiting Scholar Fund
(No. SKL2015-04) and the National Natural Science Foundation of
China (No. 51402077 and No. 61376005).
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