1096
13, JULY 1, 2019
Theoretical Design of Mid-Infrared Graphene
Optical Gas Sensor Based on
Slot Si Core Fiber
Jiaqi Wang , Yuzhi Chen, Youfu Geng , Xueming Hong, and Xuejin Li
Abstract— Silicon core optical fibers are promising for realizing
all-in-fiber optical processing and sensing applications in the
mid-infrared spectral region. However, this approach requires
integration with other optoelectronic materials to realize various
functions. Here, we theoretically designed a graphene optical
gas sensor based on silicon fibers at 8-µm wavelengths. Gas
molecules adsorbed on graphene serving as the charge-carrier
donors or acceptors change graphene’s optical conductivity,
which leads to the change in the optoelectronic properties of
graphene-integrated devices. We first optimized the Fermi level
of graphene and the operating wavelength so that the gas
molecules can effectively change graphene’s optical conductivity.
Then, we proposed a silicon slot fiber structure to enhance the
optical interaction in graphene-on-silicon fiber devices. Based on
the optimized silicon slot fiber structure, we designed a fiber-
integrated graphene Bragg grating structure, in which the 3-dB
bandwidth of the central reflection band increases linearly with
the gas concentration. Our proposed device has a detection limit
below one part per million and 90-fold improvement of sensitivity
compared with the designed graphene-on-silica microfiber gas
sensors for gaseous nitrogen dioxide detection. This letter paves
the way for the mid-infrared silicon optical fiber sensors.
Index Terms— Silicon optical fiber, graphene, Bragg gratings,
optical gas sensor.
I. I NTRODUCTION
D URING the past decade, various fabrication technologies
have been developed for making low-loss silicon (Si) core
fibers [1], [2], which are emerging as a promising platform for
the all-in-fiber vision where light can be generated, modulated
and detected within the optical fiber geometry. Compared
with conventional Si photonic integrated circuits (PICs) with
planar waveguide devices mostly constructed on silicon-on-
insulator wafers [3], silicon fibers are easier to be integrated
with optical fibers and other chip-based components. Besides,
the guiding properties can be engineered in the radial and
Manuscript received May 6, 2019; revised May 22, 2019; accepted
May 23, 2019. Date of publication May 27, 2019; date of current version
June 19, 2019. This work was supported in part by the National Science
Foundation of China under Grant 61805164 and Grant 61775149, in part
by the Natural Science Foundation of SZU under Grant 85302-000170,
in part by the Shenzhen Research Foundation for Talented Scholars under
Grant 000309, in part by the Shenzhen Science and Technology Project
under Grant JCYJ20160226192754225, Grant JCYJ20160307145209361, and
Grant JCYJ20160307111047701, and in part by the Guangdong Natural Sci-
ence Foundation under Grant 2017A010101018 and Grant 2016A030313059.
(Corresponding author: Xuejin Li.)
The authors are with the College of Physics and Optoelectronic Engineering,
Shenzhen University, Shenzhen 518061, China, also with the Shenzhen Key
Laboratory of Sensor Technology, Shenzhen 518061, China, and also with the
Shenzhen Engineering Laboratory for Optical Fiber Sensors and Networks,
Shenzhen 518061, China (e-mail: lixuejin@szu.edu.cn).
Color versions of one or more of the figures in this letter are available
online at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/LPT.2019.2919427
1041-1135 © 2019 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
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IEEE PHOTONICS TECHNOLOGY LETTERS, VOL. 31, NO.
longitudinal axis direction, adding more functionality to Si
fibers. Moreover, taking advantages of the giant third-order
susceptibility χ (3) , the absence of two-photon absorption
beyond 2.1μm wavelengths, and small core sizes in tapered
structures, nonlinear effects have been explored in silicon core
fibers [4]. Si has a broad transparency window from 1 to 8μm
which covers the fingerprint spectroscopic window correlated
to the fundamental vibrations of chemicals, making silicon
devices suitable for optical chemical sensing applications. And
there have been significant advances in optical sensors based
on Si PICs [5] in recent years. However, the development of
optical sensors based on silicon fibers is still at its infancy.
On the other hand, graphene is an important optoelec-
tronic material in developing optical sensors [6]. Graphene
is a monolayer of carbon atoms arranged in a hexagonal
lattice with low carrier density and large surface-volume
ratio, and therefore it has a large adsorption capacity. The
adsorbed molecules act as donors or acceptors, changing
the local carrier density and permittivity of graphene [6].
The change of permittivity can lead to the variation of
optoelectronic properties of graphene integrated photonic
devices, which is suitable for developing optical sensors.
However, due to the relatively weak interaction between
monolayer graphene and the normally incident light, it is
challenging to effectively probe the permittivity of graphene.
To overcome this limitation, researchers have developed sev-
eral configurations with in-plane interactions between the
propagating light and top layer graphene, such as graphene
integrated with PICs [7], [8] and graphene integrated with
silica microfibers [9]. Notably, researchers have shown great
interest in developing graphene-based optical gas sensors with
the in-plane interaction configuration which can provide high-
sensitivity and low-cost solutions for optical gas sensing, such
as graphene integrated with silica microfiber interferomet-
ric structures [10]. However, these devices should be inte-
grated with other components, for example, photodetectors or
spectrometers, to form useful products. Si fibers are promising
for realizing all-in-fiber sensing schemes, but there is little
research on graphene-on-Si fiber optical sensors.
In this letter, we present the design of graphene optical
gas sensors based on Si fibers. The Fermi level of graphene
and the operating wavelength were first investigated and
optimized. Then, we proposed the design of graphene-
on-Si slot fiber (GoSSF) structure. Owing to the optical
field enhancement in the subwavelength low refractive
index (RI) slot and less mode confinement of the fiber
mode, the light-graphene interaction is stronger in the
transverse electric (TE) mode GoSSF than in the TE-mode
graphene-on-Si microfiber (GoSMF). Since the transverse
magnetic mode is less stable than the TE mode, in the
following discussion we only studied optical characteristics of
 WANG et al.: THEORETICAL DESIGN OF MID-INFRARED GRAPHENE OPTICAL GAS SENSOR BASED ON SLOT Si CORE FIBER
Fig. 1. The relative permittivity of graphene as a function of Fermi level for
different wavelengths. (a) The real part of the relative permittivity. (b) The
imaginary part of the relative permittivity.
TE-mode graphene-on-Si fiber devices. Based on the
optimized GoSSF structure, we designed a graphene Bragg
grating. The adsorbed nitrogen dioxide (NO2 ) gas molecules
change the permittivity of graphene, leading to the change
of the effective RI of the GoSSF and therefore the change
of the reflection spectrum of the Bragg grating. The gas
concentration can be deduced from the 3dB bandwidth of
the central reflection band. Our simulation shows that the
proposed gas sensor has ninety-fold improvement of sensitivity
compared with the graphene-on-silica microfiber gas sensors.
II. O PTICAL P ROPERTIES OF G RAPHENE
Optical properties of graphene can be described in terms of
the optical conductivity, σ , which is calculated from the Kubo
formula [11]
2i e2( + 2i ) 1 n = (−0.18247 + 5.59596CN O2 +0.04481CN O2 2 )×1010,
σ =− [
h ( + 2i )2
 ∞ 2
ω + 2 δn F (ω) δn F (−ω)
× ( − )dω
 ω δω δω
 ∞ 2
ω + 2 n F (−ω) − n F (ω)
− ( )dω], (1)
 ω ( + 2i )2 − 4ω2
where h is Planck constant,  is the optical frequency, ω is the
energy of the relativistic Landau levels,  = 0 is the excitonic
gap of Landau level energies, n F (ω) = 1/[exp((ω−μc )/T )+1]
is the Fermi distribution function with μc being the Fermi
level and T = 300K being the temperature,  = eV F 2 /(μμc )
is the scattering rate with VF = 0.95×106m/s being the Fermi
velocity and μ = 15000cm2/V/s being the electron mobility.
By assuming a thickness d = 0.7nm to the monolayer
graphene [12], the relative permittivity of graphene is deduced
from [11]
σ 4π(n + n)
εe f f = 1 + i , (2)
ε0 d
where ε0 is the relative permittivity of vacuum. The com-
plex relative permittivity as a function of Fermi level at
wavelengths of 1.55μm, 3.5μm, 8μm, and 13μm is shown
in Fig. 1. When the Fermi level is less than half of the
photon energy, the relative permittivity is dominated by the
imaginary part, indicating that graphene has relative large
linear optical absorption caused by the interband transition.
When the Fermi level is larger than half of the photon energy,
the imaginary part of the relative permittivity drops towards
zero since the interband transition is blocked due to the Pauli
blocking effect. Also, as the Fermi level further increases,
the real part decreases rapidly such that the incident light can
have a significant phase shift. Besides, as shown in Fig. 1(a),
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1097
Fig. 2. The relative permittivity of graphene with different initial doping
levels in the gaseous condition at the wavelength of 8 μm. (a) The real part.
(b) The imaginary part.
within the Fermi level range from half of the photon energy
to 1eV, the slopes of the curves increases with the optical
wavelength, which shows that the real part is more sensitive
to the change of Fermi level at longer operating wavelengths.
Based on the optical properties of graphene, the gas sensor
can be designed at long operating wavelengths with a large
phase shift of input light, and at Fermi levels beyond half of
the photon energy with low optical losses. Considering the
transparency window of Si, we chose 8μm as the operating
wavelength. When graphene is exposed to a gas, the adsorbed
gas molecules can change the local carrier concentration,
which is also related to the gas species due to the selectivity
of gas adsorption in graphene. It is worth to mention that the
doping effect from the Si fiber can be negligible [7], [13]. The
chemically induced carrier concentration, n, by adsorbed
NO2 with the concentration of CNO2 (ppm), is described by
(3)
which is estimated from the experimental measurement in [6].
This experiment was conducted by diluting NO2 gas in an
inert gas at the standard atmospheric pressure and room
temperature. The variation in operating temperature can affect
the sensitivity due to the change of σ . So the proposed gas
sensor should be operated at the standard atmospheric pressure
and constant room temperature. Besides, Equation (3) should
be modified if graphene is used to sense NO2 in the air due
to possible interference from adsorbed O2 , H2 O, and other air
pollutants. Moreover, the variation in pressure and temperature
of the gas sample can affect the absolute concentration at the
surface of the proposed sensor and therefore its sensitivity. The
Fermi level of chemically doped graphene, E x , is described
by [13]

E x = VF , (4)
gv gs
where gv = 2 is the valley degeneracy, gs = 2 is the spin
degeneracy, and n is the initial carrier concentration which is
given by [13]
E i 2 gv gs
n=( ) , (5)
VF 4π
where E i is the initial Fermi level. We calculated the complex
relative permittivity of graphene with initial doping levels of
0.1eV, 0.2eV, and 0.3eV in the gaseous condition, as shown
in Fig. 2(a) and Fig. 2(b). As the gas concentration increases,
the real part and imaginary part of the complex relative per-
mittivity decreases more rapidly at lower initial doping levels.
Therefore the high-sensitivity photonic gas sensor demands
 1098
Fig. 3. Design of GoSSF. (a), (b) Schematics of GoSSF. (c) Optimization of
the slot width. (d) Simulated electric field distribution of TE mode GoSSF.
an initial Fermi level which is not too large but beyond half
of the photon energy. The initial doping level was chosen
to be 0.1eV, larger than half of the photon energy of 8μm
wavelength (0.08eV).
III. D ESIGN OF G RAPHENE - ON -S I F IBER G AS S ENSORS
Based on the optimized operating wavelength and initial
doping level of graphene, we proposed the GoSSF structure
to enhance the interaction between graphene and propagat-
ing light in the Si fiber. As shown in Fig. 3 (a) and (b),
the radius, r , of the Si core is fixed at 1.25μm. The silica
cladding of the Si fiber can be removed by wet etching
in experiment. In practice, the narrow slot pattern with a
width of w can be transferred to the silicon fiber by using
electron beam lithography (EBL) and reactive ion etching
or by using laser treatments. And then the chemical vapor
deposited (CVD) graphene on copper foil can be integrated on
the Si fiber by using the wet transferring process [12]. In the
wet transferring process, the graphene grown on copper foil is
coated with polymethyl methacrylate (PMMA) as a protecting
layer and the copper is etched away by using the solution of
ammonium persulfate. Then the graphene covered by PMMA
is transferred to the Si fiber. Next, the graphene-on-Si fiber
is placed on a glass substrate to define the Bragg grating
pattern on the PMMA layer over the slot fiber area by
using EBL and followed by O2 plasma etching. Finally, the
remained PMMA can be removed by acetone. Therefore, each
fabrication process is feasible based on currently available
techniques [2], [4], [7]–[10], [14].
To achieve high-sensitivity graphene optical sensors, we
maximized the optical interaction by simulating the optical
loss of the graphene-on-Si fiber at 0eV Fermi level and
8μm wavelength with the finite element method simulator
(COMSOL Multiphysics). The larger the optical loss factor,
the stronger the optical interaction. As shown in Fig. 3 (c),
the optical loss factor of the TE mode GoSSF is larger than
that of the TE mode GoSMF, which shows a stronger optical
interaction. This enhancement is because that the discontinuity
of electric field at the high-RI contrast interface is proportional
to the square of the ratio of RIs, which leads to the confinement
of high-intensity TE mode light in the slot region, as shown
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IEEE PHOTONICS TECHNOLOGY LETTERS, VOL. 31, NO. 13, JULY 1, 2019
Fig. 4. Design of the Bragg grating. (a) Schematic of the gas sensor.
(b), (c) Reflection spectra of Bragg gratings based on GoSSF and GoSOMF.
in the simulated electric field distribution of the proposed
GoSSF of Fig. 3(d). However, a wider slot has a larger optical
interaction area but less optical intensity. So there should be an
optimized slot width to reach the maximum optical interaction.
The optical loss factor is a function of slot width and reaches
the maximum of 0.05935dB/μm with a slot width of 360nm,
which is 2.7 times as large as that of the GoSMF. Besides,
another possible reason for the stronger optical interaction
is that the TE mode GoSSF (with calculated effective RI
of 1.40633) has less mode confinement than the TE mode
GoSMF (with calculated effective RI of 2.625936).
Based on the optimized GoSSF, we proposed a NO2 optical
gas sensor with a graphene Bragg grating structure, as shown
in Fig. 4(a). The operating wavelength is around 8μm, and
the initial Fermi level without gas is 0.1eV, which can be
achieved by using chemical doping [15] or electrical doping
methods [16]. The reflection of the Bragg grating, R, is defined
by [17]

sinh2 ( κ 2 − ρ 2 L)
R=  , (6)
cosh2 ( κ 2 − ρ 2 L) − σκ 2
2
where L is the length of the Bragg grating, which is 2mm,
κ and ρ are the ac coupling coefficient and dc coupling
coefficient which are defined as [16]
π
κ = δn e f f , (7)
λ
1 1 2π
ρ = 2πn e f f ( − )+ δn e f f , (8)
λ 2n e f f  λ
where λ is the wavelength in vacuum,  is the period of
the Bragg grating, n e f f is the average effective RI over the
Bragg grating period, δn e f f is the change of the average
effective RI over the period of Bragg grating. The calculated
effective RIs of the Si slot fiber with and without graphene
were 1.404782 and 1.406568, respectively, from the COMSOL
simulation. So  was 2844nm to get a center wavelength,
λ0 , of Bragg grating at 8000.56nm, which is defined as
λ0 = 2n e f f . The reflection spectrum without NO2 gas is
shown in Fig. 4(b), with a 3dB bandwidth of 11.83nm for
the central reflection band. Then with the calculated relative
permittivity at 0.1ppm and 20ppm NO2 gas concentration, the
 WANG et al.: THEORETICAL DESIGN OF MID-INFRARED GRAPHENE OPTICAL GAS SENSOR BASED ON SLOT Si CORE FIBER
Fig. 5. Calculated 3 dB bandwidths of the proposed graphene Bragg gratings.
effective RIs of the graphene-on-Si slot fiber were calculated to
be 1.404730 and 1.397111, respectively. As shown in the cal-
culated reflection spectra in Fig. 4(b), the 3dB bandwidths of
the central reflection bands are 11.92nm and 32.14nm for the
gas concentration of 0.1ppm and 20ppm, respectively. So the
normalized bandwidth, λ / w0 , (w0 is the 3dB bandwidth
of 0ppm condition, λ is the difference of 3dB bandwidth
between the gaseous condition and w0 ) is 0.007608 for 0.1ppm
and 1.716822 for 20ppm.
For comparison, we also designed a similar Bragg grating
based on the graphene-on-silica microfiber (GoSOMF) with
L = 8mm and a fiber radius of 1μm which was commonly
used in previous experimental studies [10]. The calculated
effective RIs of the silica microfiber with and without graphene
were 1.352770 and 1.352703, respectively. So  was 573nm to
get a center wavelength of 1550.2nm. For NO2 gas concen-
tration of 20ppm, the calculated effective RI was 1.352777.
The 3dB bandwidths of the central reflection bands are
0.108nm and 0.11nm for 0ppm and 20ppm gas concentration,
respectively, as shown in Fig. 4(c). So the normalized band-
width for the 20ppm condition is 0.019. Therefore, with the
same gas concentration of 20ppm, the sensitivity of the GoSSF
gas sensor is ninety times as large as that of the GoSOMF.
The reflection spectrum of the GoSSF Bragg grating under
different gas concentrations was calculated, as shown in Fig. 5.
The 3dB bandwidth of the central reflection band increases
linearly with the gas concentration, which shows the sensitivity
of 1.02nm/ppm, according to the linear fitting. To further
boost the sensitivity, a longer operating wavelength can be
applied, according to the previous discussion. Relative to Si,
germanium (Ge) has an extended mid-infrared transparency
window and low-loss Ge core optical fibers have been experi-
mentally demonstrated in recent years [18]. Here we designed
a graphene-on-Ge slot fiber (GoGSF) Bragg grating with the
same slot fiber geometry as the optimized GoSSF structure,
the same initial Fermi level of 0.1eV, a Bragg grating length
of 2mm, and a Bragg grating period of 4805nm to get a center
wavelength around 13μm. As shown in Fig. 5, the GoGSF
Bragg grating also has a detection limit below 1ppm and
a larger sensitivity of 2.71nm/ppm. The detection limit of
the proposed graphene optical gas sensor scheme based on
the graphene-on-slot fiber configuration can meet the Occupa-
tional Exposure Limit for NO2 in Europe (1ppm) [19].
IV. C ONCLUSIONS
In summary, we present the theoretical design of the mid-
infrared optical gas sensor based on the graphene Bragg
grating integrated with the Si slot optical fiber structure.
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1099
The optical properties of graphene in the gaseous environ-
ment was explored and optimized for gaseous NO2 detection.
To obtain high-sensitivity gas detection, we proposed and
optimized the slot-type Si core fiber structure for the maximum
interaction between the covered graphene and propagating
light in the Si fiber. With the optimized graphene-on-Si
slot fiber, a graphene Bragg grating structure with a center
wavelength around 8μm was presented. The gas concentration
can be measured from the change of the 3dB bandwidth
of the Bragg grating’s central reflection band. The proposed
gas sensor has a detection limit below 1ppm and detection
sensitivity of 1.02nm/ppm, which is 90 times larger than that
of the similar Bragg grating structure based on the graphene-
on-silica microfiber. The proposed optical gas sensor can
be realized in experiment by using standard nanofabrication
technology. This study paves the way for the semiconductor
optical fiber based optical gas sensors.
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