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Ultrasensitive N‑Channel Graphene Gas

Sensors by Nondestructive Molecular Doping
Bitnuri Kwon, Hyeonhu Bae, Hoonkyung Lee, Seunghyun Kim, Jinhyun Hwang, Hyungsub Lim,
Jung Hun Lee, Kilwon Cho, Jongpil Ye, Seungae Lee, and Wi Hyoung Lee*
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sı Supporting Information

ABSTRACT: Sensitive and selective detection of target gases is the

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ultimate goal for commercialization of graphene gas sensors. Here,

ultrasensitive n-channel graphene gas sensors were developed by
using n-doped graphene with ethylene amines. The exposure of the
n-doped graphene to oxidizing gases such as NO2 leads to a current
decrease that depends strongly on the number of amine functional
groups in various types of ethylene amines. Graphene doped with
diethylenetriamine (DETA) exhibits the highest response, recov-
ery, and long-term sensing stability to NO2, with an average
detection limit of 0.83 parts per quadrillion (ppq, 10−15), due to
the attractive electrostatic interaction between electron-rich
graphene and electron-deficient NO2. Our first-principles calcu-
lation supported a preferential adsorption of NO2 on n-doped
graphene. In addition, gas molecules on the n-channel graphene provide charged impurities, thereby intensifying the current
decrease for an excellent response to oxidizing gases such as NO2 or SO2. On the contrary, absence of such a strong interaction
between NH3 and DETA-doped graphene and combined effects of current increase by n-doping and mobility decrease by
charged impurities result in a completely no response to NH3. Because the n-channel is easily induced by a top-molecular
dopant, a flexible graphene sensor with outstanding NO2 detection capability was successfully fabricated on plastic without
vertical stacks of gate-electrode and gate-dielectric. Our gate-free graphene gas sensors enabled by nondestructive molecular n-
doping could be used for the selective detection of subppq-level NO2 in a gas mixture with reducing gases.
KEYWORDS: graphene, gas sensor, n-channel, gate-free, molecular doping, sensitivity

G raphene is a sp2-hybridized carbon honeycomb

network made up of single two-dimensional (2D)
layers of atoms.1,2 Gas sensors based on graphene
have been widely investigated because of their high specific
surface area for molecular adsorption. Graphene has excellent
grown graphene also provides a platform onto which large-
area, high-speed, and flexible gas sensors could be
fabricated.5,15 Nonspecific binding driven by van der Waals
interaction is the main reason for the adsorption of gas
molecules, and thus selective detection of gas molecules with a
electrical properties, such as high carrier mobility and low low detection limit is a target goal. Here, substitutional atomic
noise level of current, which are also advantageous for sensor doping of graphene, introduction of an edge by fabrication of
applications.3−5 In addition, it has a band structure of a Dirac graphene nanoribbon, and functionalization of graphene were
cone with zero bandgap, and its Fermi level can be easily adopted to induce specific interaction with gas molecules.16−18
changed by doping.6 Thus, graphene gas sensors have been Such defect engineering can increase the binding affinity of
developed for the detection of dipolar gases (e.g., NO2 and
target gas molecules, thereby enhancing the response of the gas
NH3) with a single molecular level.3 To commercialize the
sensor.18−21 For instance, oxygen functional groups in
graphene gas sensors for applications in air pollution sensors,
wearable exhale sensors, and artificial olfaction, large-area
fabrication of sensor array is indispensable.4,7−10 Received: September 16, 2021
Chemical vapor deposition (CVD) can yield a large-area, Accepted: January 25, 2022
high-quality, and single-layer graphene onto a Cu catalyst.11 Published: February 3, 2022
Since the synthesized graphene can be transferred to another
substrate after Cu etching, it has wide application possibilities,
especially for transparent conductive electrodes.12−14 CVD-

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Figure 1. Fabrication steps and operating principle of n-channel graphene. (a) Schematic illustration of the fabrication process of a gas
sensor based on n-doped graphene FETs with EDA, DETA, and TETA. (b) Response mechanism of n-doped graphene to NO2.
graphene created by UV ozone treatment increased sensitivity
to target gases.22 However, the sp2-hybridized carbon honey-
comb network can be destroyed, and surface defects change
the band structure of the Dirac cone while suppressing the
carrier mobility of graphene.23,24 Furthermore, recovery is
difficult owing to the high adsorption energy of such defects.
Thus, defect engineering of graphene can have drawbacks for
the fast and reversible detection of a target gas.
Charge-transfer doping can be achieved by introducing
heteromolecules near the graphene surface. It is advantageous
to induce nondestructive doping of graphene by barely
sacrificing charge carrier mobility.6,25,26 A molecular dopant
with electron-donating or electron-withdrawing character can
increase electron or hole carrier density in graphene for
decreasing sheet resistance of transparent conductive electro-
des prepared by CVD-grown graphene.27,28 However, the
effects of molecular doping on the gas-sensing properties of
graphene have not been studied extensively. Although
enhanced sensitivity to NH3 using molecular p-doping and
adverse effects of p-doping from oxygen and water molecules
to NO2 sensing were recently reported, the influence of
molecular n-doping on sensing air pollutants (e.g., NO2, SO2,
NH3) needs further studies.26,29 NO2 is a toxic exhaust gas
from air pollutants, and it is detrimental to human health
mainly due to the strong oxidizing power. Thus, continuous
monitoring of its concentration below ppm or ppb levels is
indispensable for NO2 related disease prevention.30 Because
reducing gases (e.g., NH3) as well as oxidizing gases (e.g., NO2,
SO2) are mixed in air pollutants, the cross-sensitivity test is
especially important for the real application of sensors in gas
mixture. Recently, nondestructive molecular n-doping, which
did not decrease carrier mobility of graphene, was developed
for application in transparent conductive electrode.31 It is very
interesting to examine the sensing modality of electron-rich n-
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doped graphene to various types of air pollutant gases. Also,
the adsorption behavior of target gas on n-doped graphene
needs to be supplemented by theoretical calculations, as
sensitivity is proportional to the gas adsorption. Furthermore,
charged impurity scattering from adsorbed gas molecules
should be taken into account for interpreting change in
electrical properties resulting from charge transfer at
graphene−gas molecule interface.
In this study, CVD-grown graphene was n-doped with
ethylene amines by vapor-phase molecular doping, which is a
strong, stable, uniform, and nondestructive doping method.31
The amine functional group is widely used as an electron
donor in numerous studies, so it is suitable for the n-doping of
graphene.32−35 Ethylenediamine (EDA), diethylenetriamine
(DETA), and triethylenetetramine (TETA) with two, three,
and four amine functional groups, respectively, were used for
comparative analysis. Graphene doped with ethylene amines is
rich in electrons, and the n-channel graphene sensor was
utilized in sensing oxidizing gases such as NO2. Although gas
sensing performance was measured by a chemiresistive manner
without gate-bias, field-effect mobility as well as Dirac point
shift as a result of gas exposure were monitored by
constructing with graphene field-effect transistors (FETs) on
SiO2/Si. We could examine the effects of charge transfer at the
adsorbed gas molecule−graphene interface and charged
impurity scattering simultaneously due to FET measurement.
It has been shown that electron-rich graphene has a remarkable
response to electron-deficient NO2 by the attractive electro-
static interaction and subsequent charge transfer and charged
impurity scattering. A cross-sensitivity test was also conducted
to verify the sensing modality of n-doped graphene with SO2
and NH3. Theoretical calculation confirmed that concentration
of electron doping affects adsorption of NO2 and NH3
differently. Importantly, an average limit of detection (LOD)
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of 0.83 parts per quadrillion (ppq, 10−15) was realized with a point is far below 0 V and the majority of charge carriers in n-
DETA-doped graphene gas sensor, which was not attainable in doped graphene are electrons at the zero-gate bias. Thus,
the bare graphene gas sensor before n-doping. Finally, flexible response to oxidizing gas such as NO2 could be facilitated by
chemiresistive sensor with excellent NO2 detection capability the electrostatic interaction between electron-rich graphene
was fabricated on plastic without vertical stacks of gate- and electron-deficient NO2 (Figure 1b, left). Because our n-
electrode and gate-dielectric. channel graphene sensor responds differently to types of target
gases, dynamic measurement of current at the zero-gate bias
RESULTS AND DISCUSSION could be used to detect traces of NO2 target gas (Figure 1b,
A schematic illustration of the fabrication steps for the right).
graphene gas sensor using n-doping is shown in Figure 1a. The characteristics of the n-doped graphene were analyzed
The SiO2/Si substrate has charged impurities on the surface, by Raman spectroscopy using a 532 nm laser with 1 mW
and defects in the SiO2 layer facilitate the adsorption of power to minimize damage to the graphene (Figure 2a). All
moisture and oxygen in the atmosphere.36 For this reason, the spectra exhibited a small D peak, and the intensity of D
graphene on SiO2/Si is generally p-doped. To block these peak did not increase after molecular doping, which indicates
impurities and reduce the substrate-induced doping of that the defects were not generated under the molecular
graphene, the SiO2/Si substrate was treated with hexamethyl- doping process (Figure S1 in the Supporting Information).
disilazane (HMDS) prior to the transfer of CVD-grown Charge-transfer doping of graphene can be analyzed using the
graphene.37,38 Vapor-phase molecular doping with three types relative ratio of the 2D versus G peak (I2D/IG) and the
of ethylene amines (EDA, DETA, and TETA) was performed bandwidth of the 2D peak (full width at half-maximum (fwhm)
for the n-channel graphene gas sensors. The characteristics of of the 2D peak).39 In the order TETA > DETA > EDA, I2D/IG
ethylene amines are listed in Table 1. The detailed procedure decreases, and the fwhm of the 2D peak increases (Figure 2b
and Table 2). As the number of amine functional groups
Table 1. Characteristics of the Three Types of Ethylene increase, the doping concentration increases. In addition, the
Amines60 position of the G peak in the vicinity of 1580 cm−1 shifts to a
higher wavenumber as a result of molecular doping. The AFM
vapor pressure images in Figure S2 show uniformly distributed doping
molecular boiling at 20 molecules on a large-area graphene, which agrees with the
no. weight point °C at 70 °C at 120 °C uniformity seen in the Raman spectra. The electrical
amines (g mol−1) (°C) (Pa) (Pa) (Pa)
characteristics of the graphene transistors before and after
EDA 2 60.1 116.9 1300 20,000 114,000 molecular doping were analyzed to verify the type of doping
DETA 3 103.2 206.7 10 460 5700 (Figure 2c). The Dirac point voltages were measured to be
TETA 4 146.2 276.5 <1 13.5 400 43.3 ± 1.2, −135.7 ± 3.3, −157.7 ± 3.9, and −177.7 ± 3.9 V
for bare, EDA-, DETA-, and TETA-doped graphene,
for vapor-phase molecular doping is provided in the respectively (Table 2). This result proves that the electron-
Experimental Section. The n-channel indicates that the Dirac donating effect in ethylene amines is responsible for the n-

Figure 2. Doping properties of graphene. (a) Raman spectra of bare, EDA-, DETA-, and TETA-doped graphene on HMDS treated SiO2/Si.
(b) I2D/IG and fwhm of 2D peak. (c) Transfer characteristics of graphene FETs at VDS of 0.01 V. (d) The extracted Dirac point voltage
(VDirac) and n-type carrier mobility.

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Table 2. Raman Spectra and Electrical Characteristics of Bare, EDA-, DETA-, and TETA-Doped Graphene
doping material I2D/IG 2D peak fwhm (cm−1) Dirac point voltage (V) charge carrier densitya (1012 cm−2) n-type mobility (cm2/(V s))
bare 1.66 ± 0.13 43.91 ± 0.88 43.3 ± 1.2 3.1 (hole) 563 ± 24
EDA 1.37 ± 0.08 46.24 ± 1.39 −135.7 ± 3.3 9.8 (electron) 987 ± 90
DETA 1.11 ± 0.13 48.91 ± 0.97 −157.7 ± 3.9 11.4 (electron) 977 ± 68
TETA 0.75 ± 0.03 50.01 ± 3.99 −177.7 ± 3.3 12.8 (electron) 802 ± 113
a
Calculated from average Dirac point voltage (VDirac) and n = αVDirac, where α is 7.2 × 1010 cm−2 V−1.

Figure 3. Gas sensor performance of n-channel graphene. (a) NO2 sensing characteristics of bare, EDA-, DETA-, and TETA-doped graphene.
(b) The extracted response and recovery. Characteristics of graphene gas sensors over time exposed to the atmosphere. Stabilities of (c)
EDA-doped, (d) DETA-doped, and (e) bare graphene by exposing the devices to the atmosphere. (f) Summary of response changes with
exposure time.

doping and the concentration of n-doping is directly related to
the number of amine functional groups. The hole and electron
mobilities of the bare graphene field-effect transistor (FET)
were 1821 ± 91 and 563 ± 24 cm2/(V s), respectively. The
relatively low electron mobility in graphene can be explained
by the suppression of electron conduction under the prevailing
p-doping. After doping with EDA, DETA, and TETA, the
electron mobilities were 987 ± 90, 977 ± 68, and 802 ± 113
cm2/(V s), respectively (Figure 2d and Table 2). The increase
in electron mobility after doping with ethylene amines can be
explained by the asymmetry in carrier conduction as a result of
the change in the doping type from p-doping to n-doping.40
2179
The characteristics of the graphene gas sensors were
investigated by measuring the current in the channel while
the gate voltage was fixed at 0 V. The device was exposed to
NO2 at a concentration of 50 ppm for 5 min and then purged
with nitrogen for 30 min. This process was repeated twice. The
responses of the gas sensors according to molecular doping are
shown in Figure 3a and summarized in Figure 3b and Table 3.
Because NO2 is an oxidizing gas, the adsorption of NO2 leads
to the generation of hole carriers (i.e., p-doping). However, p-
doping has different effects on bare graphene and n-doped
graphene. The main carriers of bare graphene are holes, and
the current in the channel increases with additional hole
carriers generated by NO2. In contrast, graphene after doping
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Table 3. NO2 Sensing Characteristics of Bare, EDA-,
DETA-, and TETA-Doped Graphene
doping material response (%) recovery (%)
bare 10 ± 1.8 55 ± 4.7
EDA −77 ± 2.6 −38 ± 6.6
DETA −76 ± 0.5 −75 ± 5.9
TETA −56 ± 2.9 −44 ± 9.9
with ethylene amines has the characteristic of an n-type
semiconductor under the gate-free condition, so when NO2
induced p-type doping occurs, the current in the channel
decreases. The absolute response in the gas sensor falls in the
order: DETA > EDA > TETA > bare. Because the electron
carriers generated under molecular doping interact closely with
NO2 with electron-withdrawing character, the adsorption of
NO2 on n-doped graphene can be facilitated between electron-
deficient NO2 and electron-rich graphene.41 Thus, n-doped
graphene exhibits better NO2 sensing performance than p-
doped graphene. As the magnitude of n-doping increases from
EDA-doped graphene to DETA-doped graphene, the adsorp-
tion strength of NO2 on n-doped graphene increases. However,
a further increase in the doping strength to TETA results in a
decrease in its absolute response. This is because the electron
mobility of TETA-doped graphene is lower than that of EDA-
or DETA-doped graphene (Figure 2d). We speculate that
DETA is the optimal dopant in terms of compromise between
adsorption strength and electron mobility. Interestingly, the
graphene sensor doped with DETA exhibited the highest
recovery. Compared to DETA and TETA molecules, EDA
molecules with the highest vapor pressure can be removed by a
purging gas; thus, graphene cannot recover the initial state of
n-doping after removing NO2 target gases. In contrast, the
binding of NO2 to TETA-doped graphene is exceptionally
high, so NO2 on TETA-doped graphene cannot be removed
even under purging conditions. These adverse effects are not
dominant in DETA-doped graphene, thereby enabling
reversible sensing characteristics with the highest response
and recovery. We also speculate that excellent recovery in
DETA-doped graphene might be due to the covering of the
defects (i.e., grain boundaries) in CVD-grown graphene with
DETA molecules. Such defects may need high desorption
energy for the reversible detachment of target molecules.42
To evaluate the stability of the n-doped graphene gas
sensors, the gas sensors were measured after exposing the
devices to ambient air for 14 days. The experiment was
conducted with graphene gas sensors doped with EDA and
DETA, which have relatively high response characteristics, and
a bare graphene gas sensor for comparison (Figure 3c−f and
Table 4). As the exposure time to ambient air increases, the
responses of the bare and EDA-doped graphene gas sensors
Table 4. Stabilities of NO2 Sensing Characteristics of Bare, EDA-, and DETA-Doped Graphene by Exposing the Devices to the
Atmosphere
bare
exposure time response (%) recovery (%)
immediately 7 56
after 1 day 15 26
after 2 days 11 13
after 7 days 10 25
after 14 days 9 33
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decrease, and in particular, EDA-doped graphene shows a rapid
decrease in response. The low stability of the EDA-doped
graphene gas sensor is directly linked to the high vapor
pressure of EDA even at 20 °C (Table 1). In contrast, the
DETA-doped graphene gas sensor maintains an absolute
response of 70%, even when exposed to ambient air for 14 days
(Figure 3f), that is, it has only decreased by 9% since exposure
to the atmosphere. This outstanding performance is directly
linked to the extremely low vapor pressure of DETA at 20 °C,
which is more than 2 orders of magnitude lower than that of
EDA. Furthermore, DETA molecules may bind strongly with
defects in graphene, thereby additionally increasing doping
stability. Accordingly, the reversible attachment and detach-
ment of NO2 are feasible on DETA-doped graphene.
Because the transferring process of CVD-grown graphene to
target substrate typically led to polymer residue remaining on
the graphene surface (Figure S2a), the effect from polymer
residue needs to be verified in the n-doped graphene gas
sensor. Thus, the residue was removed by thermally annealing
the transferred graphene at 350 °C (H2/Ar conditions), and
the gas sensor performance before and after DETA doping was
compared.43 Figure S3a shows the AFM image of the thermally
treated graphene, which has a clean surface with a few wrinkles
and a small amount of residue. When electrical properties of
graphene FETs were measured, the Dirac point was no longer
detected (Figure S3b). This huge p-type doping of graphene is
caused by the activated process of charge transfer under
thermal treatment.44 The uniform doping with a Dirac point
voltage of −108 V was accomplished after DETA doping on
the clean graphene (Figure S3b,c). The clean graphene sensor
exhibited a weaker response (2%) than the graphene without
the cleaning step (10%), mainly due to the substantial decrease
in the carrier mobility (∼114 cm2/(V s)) under p-doping
(Figure S3d and Figure 3a). DETA-doped clean graphene
exhibited an outstanding absolute response of 50%, which is
slightly lower than 77% in DETA-doped graphene without the
cleaning step. This can be explained by judging from the lower
n-doping level in DETA-doped clean graphene. Thus, the n-
doping level rather than the residue in the graphene surface
dominantly affects the response of graphene toward NO2.
Although polymer residue covers the transferred CVD-grown
graphene surface, DETA can sufficiently n-dope the graphene
for inducing attractive electrostatic interaction toward NO2.
The validation of our n-channel gas sensor was further
examined in graphene gas sensors with different metal contacts
(Figure S4). The n-channel graphene gas sensors exhibited
excellent performance regardless of the metal contacts used
(e.g., Au, Ag, Al, Pt).
Selective detection of NO2 is required to reduce the
unwanted signals from gas mixtures in real atmospheric
conditions. Figure 4 and Table 5 show the cross-sensitivities
EDA DETA
response (%) recovery (%) response (%) recovery (%)
−73 −29 −77 −76
−51 −45 −72 −74
−51 −42 −74 −61
−50 −37 −73 −58
−32 −52 −70 −38
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character. NH3 has an electron-donating character, thereby

Figure 4. Cross-sensitivity of graphene sensors. (a) Gas sensing
characteristics and (b) summarized responses of bare graphene.
(c) Gas sensing characteristics and (d) summarized responses of
DETA-doped graphene.
Table 5. Cross-Sensitivities of Bare and DETA-Doped
Graphene Sensors under Various Target Gases (NO2, SO2,
NH3)
NO2 SO2 NH3
bare 11 3 −0.3
response (%)
DETA −77 −17 0 adsorption of NO2 on n-doped graphene, the charge density
and summarized responses of the bare graphene and DETA-
doped graphene. The gas sensor test was conducted with 50
ppm of NO2, SO2, and NH3 target gases, and the responses of
bare graphene to each gas were 14%, 3%, and −0.3%,
respectively (Figure 4a,b). The response of SO2 to graphene is
much lower than that of NO2, which is related to the lower
oxidizing strength of SO2. The response signal of NH3 is
opposite to that of NO2 or SO2 because of its reducing
inducing the n-doping of graphene. The responses of DETA-
doped graphene to each gas were −77%, −17%, and 0%,
respectively (Figure 4c,d). DETA-doped graphene has a much
higher absolute response to NO2 and SO2 than bare graphene
without molecular doping. Because SO2 is an oxidizing gas
with a lower oxidizing power than NO2, a similar sensing
mechanism for SO2 can be applied to its enhanced sensing
signal in DETA-doped graphene. It should be emphasized that
the selectivity of DETA-doped graphene to NO2 versus NH3
target gas is much higher than that of bare graphene, mainly
because of its extremely high sensitivity to NO2 and no
response to NH3 (Figure S5).
To explain the selective adsorption of NO2 on n-doped
graphene, we performed the first-principles calculations for the
adsorption of these gases on graphene as a function of the
electron-doping concentration. The electron-doping concen-
tration was varied from the neutral state to dense condition
(∼1.2 × 1014 e/cm2, which is equivalent to the one electron
per 32 carbon atoms (4 × 4 supercell of primitive cell)). The
calculated adsorption energies of NO2 and NH3 are shown in
Figure 5a using eq 6. We found that the decrease in adsorption
energy of NO2 becomes larger as the electron-doping
concentration increases, whereas the decrease in the
adsorption energy of NH3 is negligible. We also performed
thermodynamic analysis using the eq 7. Pressure and
temperature were set to 50 ppm and 300 K to emulate the
experimental situation. We then calculated the fractional
occupancy (f) of NO2 and NH3 gases at certain electron-
doping concentrations. The fractional occupation of NO2
significantly increases as the electron-doping concentration
increases, whereas the change in the fractional occupancy of
NH3 is negligible (Figure 5b). This agrees well with our
experimental observation of selective adsorption of NO2 on n-
doped graphene. To study the origin of the selective
differences in the case of NO2 and NH3 were calculated, as
shown in Figure S6. Figure 5a inset shows that the difference in
the charge between the NO2 molecule and the doped graphene
sheet becomes significantly increased compared with that for
the pristine graphene. In contrast, the difference in the charge
for doped graphene by NH3 adsorption is not significantly
increased. This reveals that the electrostatic interaction by the
electron doping in graphene is more significant with NO2
adsorption than with NH3 adsorption. Therefore, we believe

Figure 5. Theoretical calculation. (a) Calculated adsorption energies of NO2 (black, square) and NH3 (red, circle) on the n-type doped
graphene monolayer as a function of the electron-doping concentration. (b) Calculated occupancies (surface coverage) of NO2 and NH3 as a
function of the electron-doping concentration under 50 ppm and 300 K.

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Figure 6. Effects of charged impurities. Transfer characteristics and n-type mobilities of DETA-doped graphene FETs under 5 ppm of NO2
(a, d) and 0.1 ppm of NO2 (b, e) and 50 ppm of NH3 (c, f). VDS is fixed at 0.01 V.

that this enhanced charge transfer between n-doped graphene transistors under the exposure of 5 ppm of NO2 and 0.1 ppm
and NO2 contributes to the ultrasensitive detection of NO2 in of NO2 are shown in Figure 6a,b, respectively. At both NO2
the n-doped graphene sensor. concentrations, field-effect mobilities of DETA-doped gra-
We also observed that the NO2 molecules on the n-channel phene decrease abruptly (Figure 6d,e). This effect intensifies
graphene provide charged impurities, thereby boosting the the current decrease significantly under NO2 exposure, thereby
response by reducing its electron mobility (Figure 6 and Table resulting in an excellent response to oxidizing gases such as
6). The transfer characteristics of DETA-doped graphene NO2 or SO2. The effect of charged impurities from NO2 is
reversible because NO2 molecules could be easily removed by
Table 6. N-Type Mobility of DETA-Doped Graphene FETs purging gas. Accordingly, n-type mobility with purging time
under 5 and 0.1 ppm of NO2 Exposure restores quickly to the value before NO2 injection (Figure S7).
N-type mobility (cm2/(V s)) In contrast, the adsorption of DETA-doped graphene to
reducing gases such as NH3 could not be facilitated by the
time NO2 time NO2 time NH3
(s) (5 ppm) (s) (0.1 ppm) (s) (50 ppm) repulsion between lone pair electrons in NH3 and electron-rich
0 530 0 695 0 507 n-doped graphene. Thus, the nitrogen atom in NH3 is
30 381 30 629 120 502 preferentially located at the top when approaching the n-
600 380 60 614 300 494 doped graphene (Figure S6d). Although NH3-driven n-doping
1200 375 300 613 600 481 in the DETA-doped graphene induced a shift in Dirac point
voltage and a corresponding small increase in current (Figure
6c), surprisingly the DETA-doped graphene showed no
response to NH3 (Figure 4c and Figure S5). This might be

Figure 7. LOD of graphene sensor. (a) Gas sensing characteristics of bare and DETA-doped graphene at various NO2 concentrations. (b)
Plot of response versus gas concentration.

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Figure 8. Flexible graphene sensor. (a) Device image. (b) Gas sensing characteristics of bare and DETA-doped graphene on a flexible
substrate under 1 ppm of NO2.
caused by the dilution effect of current increases by the
scattering from charged impurities. Note that the NH3
molecules on graphene can also be charged impurities, as
shown in the decrease of n-type mobility (Figure 6f). The n-
channel operation of graphene was advantageous for boosting
sensitivity to oxidizing gases with a small signal perturbation to
reducing gases.
The LOD was measured with DETA-doped graphene to
verify ultrasensitive detection of NO2. The response of DETA-
doped graphene was compared with bare graphene under an
NO2 concentration of 0.4 ppm to 0.06 ppm (Figure 7a). The
bare graphene gas sensor hardly detects NO2 target gas under
these conditions (see black curve in Figure 7a), but the DETA-
doped graphene gas sensor detects it accurately and shows a
high response of −29% even at 0.06 ppm. Although the lowest
NO2 limit in the experimental system is 0.06 ppm, the LOD
can be extracted from the measured sensor’s signal-to-noise
ratio in the procedure described in the Experimental Section.45
The average LOD of the DETA-doped graphene gas sensor
was calculated to be 0.83 ppq from 4 devices, while the lowest
LOD extracted was 0.58 ppq (Figure 7a and Figure S8). This
value is the lowest LOD of NO2 sensors reported so far for
graphene gas sensors, while most of works remain in the level
of ppb (see Table S1). We noticed only two recent works that
reported subppt detection of NOx using in situ cleaned
ultraclean graphene and epitaxial graphene, respectively.46,47
Although we fabricated the sensor with a poly(methyl
methacrylate) (PMMA) assisted transfer process using scalable
CVD-grown graphene and operated the graphene sensor at
room temperature, the LOD of our sensor is approximately 3
orders of magnitude lower than the lowest reported LOD. We
additionally conducted theoretical calculations to rationalize
such low detection capability of graphene (Figure S9). By
using a modified exchange−correlation functional, subppq-
level detection capability of our n-channel graphene could be
validated (see explanation in Figure S9).
To prove the potential of our n-channel graphene sensor,
CVD-grown graphene is transferred to the polyethylene
naphthalate (PEN) substrate, and the flexible gas sensor was
fabricated by simply depositing electrodes on a graphene sheet.
Vapor phase molecular doping was applied on graphene/PEN
by following a similar process in Figure 1a. The device image in
Figure 8a shows the flexibility of our n-channel graphene
sensor. The flexible graphene sensor before molecular doping
(bare) exhibited no response to 1 ppm of NO2, while the
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DETA-doped flexible graphene sensor exhibited an extremely
high response of −80% as well as excellent recovery under the
same condition (Figure 8b). When the response curve was
fitted according to the change in normalized resistance, our n-
channel sensor showed an extremely high response (>400%)
(Figure S10). Because our sensor does not have a gate-
dielectric and gate-electrode, the device structure is simpler
than the transistor-type sensor. It has been reported that the
transistor-type sensor is advantageous to enhance the
sensitivity of gas sensors.10,48 The gate bias can control the
charge carriers at the semiconductor−dielectric interface,
which can be used to amplify the sensing signal.49 In the
transistor-type sensor, however, it is difficult to find a suitable
gate-dielectric for both high dielectric strength and mechanical
flexibility.50,51 In addition, low-voltage operation is typically
hampered by the low capacitance of the gate-dielectric. In our
sensor, the vapor phase n-doping induces sufficient electrons at
the channel region while enabling sensitive and selective
detection of NO2 by attractive electrostatic interaction. We
believe that the gate-free chemiresistive graphene sensor is
more suitable for the flexible gas sensing platform. Our n-
channel graphene sensor can also be sensitively operated at
synthetic air conditions with high relative humidity, proving
the availability of our sensor in ambient conditions (Figure
S11).
CONCLUSION
The gas sensor performance of the graphene FET was
improved by molecular n-doping with ethylene amines having
two, three, and four amine units (EDA, DETA, and TETA).
Although the magnitude of n-doping order is as follows: TETA
> DETA > EDA, the absolute response to NO2 target gas order
is as follows: DETA > EDA > TETA > bare (pristine
graphene). Because graphene doped by ethylene amine is
operated in the n-channel region, the source−drain current in
zero gate-bias decreases upon exposure to an oxidizing gas
such as NO2. DETA was an optimum doping condition for the
enhanced response and recovery as well as long-term sensing
stability. The cross-sensitivity test revealed that DETA-doped
graphene exhibits completely no response to NH3. Theoretical
calculations revealed that the selective adsorption of NO2 on n-
doped graphene is caused by the attractive electrostatic
interaction between electron-rich n-doped graphene and
electron-deficient NO2. Furthermore, the abrupt decrease of
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mobility upon NO2 exposure further enhanced the sensitivity
to NO2 in DETA-doped graphene. Accordingly, the graphene
doped by DETA showed an extremely low average LOD of
0.83 ppq. Flexible graphene gas sensor with excellent response
to NO2 was demonstrated with gate-free architecture by
applying simple vapor phase n-doping. We have confirmed that
n-channel operation of graphene by molecular n-doping is the
key to improve the sensitivity and selectivity to oxidizing gases
with a small signal perturbation to reducing gases.
EXPERIMENTAL SECTION
Graphene Synthesis and Transfer. High-quality monolayer
graphene was grown on Cu foil by a CVD method, as reported
previously.11,12 A silicon wafer with 300 nm thickness of thermally
grown SiO2 purchased from Fine Science was cleaned with acetone,
isopropanol, and distilled water. HMDS purchased from Sigma-
Aldrich was spin coated on SiO2/Si that had been previously treated
with UV/ozone for 30 min. The HMDS-treated SiO2/Si was heat
treated at 120 °C for 40 min, followed by sonication in toluene for 30
s to remove residual HMDS molecules. Graphene on Cu foil was
transferred onto the HMDS-treated SiO2/Si by using a PMMA
supporting layer. The Cu layer on the back of the graphene was
etched by floating PMMA/graphene in 0.05 M ammonium persulfate
solution. When the copper was completely dissolved in the aqueous
solution and removed, washing was performed twice with distilled
water for 20 min to remove the residual etching solution. Free-
standing graphene in distilled water was carefully transferred to the
HMDS-treated SiO2/Si and treated surface with an N2 gun. The
transferred graphene with PMMA was heat treated overnight at 120
°C to increase the adhesion, and finally, the PMMA layer was
removed with acetone.
Sensor Fabrication. To fabricate graphene FETs, Au source/
drain electrodes were thermally evaporated at a rate of 0.1 nm/s with
a metal mask. The source/drain electrodes were formed such that the
channel length of the transistor was 0.1 mm and the width was 2 mm.
The highly doped silicon substrate was used as the gate electrode, and
a thermally grown silicon oxide layer (300 nm) was used as a
dielectric layer. Subsequently, EDA-, DETA-, and TETA-doping
molecules purchased from Aldrich were transferred onto the graphene
surface by evaporating them on a hot plate (Figure 1). The EDA and
DETA molecules were evaporated at 70 °C. In contrast, a high
temperature of 120 °C was applied to evaporate the TETA molecules,
mainly because of the low vapor pressure of TETA compared to EDA
and DETA (Table 1). Flexible sensor was fabricated on the PEN
(from DuPont) substrate by applying transfer and doping processes of
graphene similar to the silicon substrate.
Characterization. The degree of doping and the quality of
graphene were examined using Raman spectroscopy equipped with a
532 nm laser of 1 mW intensity (WITech, ALPHA300 R). The
surface morphology of the graphene films was characterized using
AFM (Park Systems, NX-10) to confirm the uniformity of the
molecular doping. The performance of the graphene transistors was
measured by collecting current−voltage characteristics with a probe
station (MS TECH, MST-M5VC) and a semiconductor character-
ization system (Keithley, 4200-SCS). The gas sensor characteristics
were measured using a built-in gas sensor setup (Precision Sensor
System Inc., GASENTEST). The gate, source, and drain electrodes of
the graphene transistors were connected to a gas sensor module using
silver wire and silver paste. The gas sensor measurement was
conducted under the gate-free condition (VDS = 0.01 V and VG = 0 V)
by flowing target gases (i.e., NO 2 , SO 2 , NH 3 ) at various
concentrations. The response and recovery of the manufactured gas
sensor were calculated using eqs 1 and 2:
response = (IG − I0)/I0 × 100(%) (1)
recovery = (IR − IG)/(IG − I0) × 100(%) (2)
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where IG is the current after injection of the target gas, IR is the
current after recovery by purging the chamber for 30 min, and I0 is the
current before injection of the target gas. Sensor noise can be
calculated using the change in relative conductance from the baseline
with the root-mean-squared deviation. Ten data points were taken
from the baseline prior to NO2 exposure. After plotting the data, the
statistical parameters of a polynomial fit as well as a curve-fitting
equation with a fifth degree polynomial fit were run within the range
of the data points using eq 3:
Vχ2 = ∑ (yi − y)2 (3)
where yi is the measured data point, and y is the corresponding value
calculated from curve fitting. The rmsnoise is calculated from eq 4:
Vχ2
rmsnoise =
N (4)
where N is the number of data points used for fitting. The sensor
noise was 17 × 10−9 for the NO2 sensor. According to the IUPAC
definition, a signal is considered to be a real signal when the signal-to-
noise ratio is 3. Therefore, the LOD can be extracted from the linear
fitting when the signal is three times that of the noise, as stated in eq
5:
rmsnoise
LOD (ppb) = 3
slope (5)
First-Principles Calculation. The degree adsorption energies of
NO2 and NH3 with respect to the electron doping concentration in
graphene monolayer were calculated by first-principles calculations in
the framework of the density functional theory (DFT)52 as
implemented in the Vienna ab initio simulation package, with the
projector-augmented wave method.53 The exchange−correlation
functional parametrized by Perdew−Burke−Ernzerhof (PBE) based
on the generalized gradient approximation was used.54 The zero-
damping DFT-D3 method by Grimme et al.55 was adopted to
compensate for the underestimated adsorption energies in the
physisorption process. Anionic states that have excess electrons in a
unit cell were implemented by regulating homogeneous background
charge densities. A kinetic cutoff energy of 400 eV was used for the
plane-wave basis set. The 4 × 4 hexagonal supercell of primitive
graphene unit cell was used in our calculation, whose composition of
the supercell is C32. A vacuum slab of ∼15 Å from the graphene sheet
was inserted along a perpendicular direction to avoid the interaction
between the graphene monolayers in periodic cell scheme. The 2 ×2
in-plane mesh within the Monkhorst−Pack scheme was set for the
Brillouin zone integration.56 Electronic and ionic optimizations were
performed until the total energy difference and Hellman−Feynman
forces reach below 10−6 eV and 0.01 eV/Å, respectively.
Adsorption energy of a gas molecule for doped graphene, Eads, was
calculated as:
δ−
Eads = Ecomplex δ−
− Egraphene 0
− Emolecule (6)
− −
where Eδcomplex and Eδgraphene indicate the total energies of adsorbate−
adsorbent complex and graphene monolayer in the neutral state or
specific anionic state, respectively, and E0molecule is the total energy of
adsorbed molecule in a neutral state, because it is supposed to
approach the neutral or anionic adsorbent from the surrounding gas.
Thermodynamic Calculation. Evaluation of adsorption energies
of NO2 and NH3 was performed by estimating the surface coverage
using the grand partition function.57 By statistical thermodynamics,
the fractional occupancy for a single adsorption site, f(P,T), is
determined by:
e(μ(P , T ) − Eads)/ kBT
f (P , T ) =
1 + e(μ(P , T ) − Eads)/ kBT (7)
where P, T, and kB indicate the pressure and temperature of
surrounding gas and the Boltzmann constant, respectively, μ(P,T) is
the chemical potential of a gas at a given P and T, and Eads is the
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ACS Nano www.acsnano.org
adsorption energy obtained by DFT calculations. Excess parts of the
chemical potential of NO2 and NH3 gases were parametrized by
regression analysis with the thermochemical data from NIST standard
reference databases 1358 and 2359, as expressed:
μreal (P , T ) = μideal (P , T ) + (A + B × T )
(8)
where μideal(P,T) denotes the chemical potential of ideal gas model,
constants A and B in linearized excess parts are 0.04993 eV and
−0.89722 meV/K for NO2 and 0.04871 eV and −0.53541 meV/K for
NH3, with R2 = 0.999 in a range from 1 atm to 1 μatm and 220 to 500
K, respectively. The pressure-dependent term in an excess part is
negligible in this range.
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsnano.1c08186.
Supporting Figures show magnified Raman spectra (S1),
AFM images (S2), doping properties and NO2 responses
with clean graphene (S3), effects of metal contact (S4),
NH3 response with DETA-doped graphene (S5), charge
density profiles of neutral and doped graphene with NO2
or NH3 (S6), transfer characteristics of DETA-doped
graphene under NO2 recovery and extracted mobility
change (S7), extraction of LODs from three sensors
(S8), NO2 adsorption energy calculated from PBE-D3
and LDA level of theory (S9), gas sensing performance
of DETA-doped graphene according to the change in
normalized resistance (S10), and gas response of DETA-
doped graphene under synthetic air (S11). Table S1
shows the summary of recently reported graphene based
NO2 gas sensors (PDF)
AUTHOR INFORMATION
Corresponding Author
Wi Hyoung Lee − Department of Organic and Nano System
Engineering, Konkuk University, Seoul 05029, Korea;
Division of Chemical Engineering, Konkuk University, Seoul
05029, Korea; orcid.org/0000-0002-2380-4517;
Email: whlee78@konkuk.ac.kr
Authors
Bitnuri Kwon − Department of Organic and Nano System
Engineering, Konkuk University, Seoul 05029, Korea
Hyeonhu Bae − Department of Physics, Konkuk University,
Seoul 05029, Korea; orcid.org/0000-0001-7276-6636
Hoonkyung Lee − Department of Physics, Konkuk University,
Seoul 05029, Korea; orcid.org/0000-0002-6417-1648
Seunghyun Kim − Department of Chemical Engineering,
Pohang University of Science and Technology, Pohang 37673,
Korea
Jinhyun Hwang − Department of Organic and Nano System
Engineering, Konkuk University, Seoul 05029, Korea
Hyungsub Lim − Department of Chemical Engineering,
Pohang University of Science and Technology, Pohang 37673,
Korea
Jung Hun Lee − Department of Materials Science and
Engineering, Seoul National University, Seoul 08826, Korea
Kilwon Cho − Department of Chemical Engineering, Pohang
University of Science and Technology, Pohang 37673, Korea;
orcid.org/0000-0003-0321-3629
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Article
Jongpil Ye − Department of Materials Science and
Engineering, Inha University, Incheon 22212, Korea;
orcid.org/0000-0002-3753-532X
Seungae Lee − Division of Chemical Engineering, Konkuk
University, Seoul 05029, Korea; orcid.org/0000-0003-
4819-7239
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsnano.1c08186
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was supported by Korea Institute for Advancement
of Technology (KIAT) grant funded by the Korea Govern-
ment (MOTIE) (P0012770) and grants from the Basic
Science Research Program of the National Research
Foundation of Korea (NRF) funded by the Ministry of
Science and ICT (2019R1A2C1010723).
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