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Cite This: ACS Nano 2018, 12, 986−993 www.acsnano.org

Metallic Ti3C2Tx MXene Gas Sensors with

Ultrahigh Signal-to-Noise Ratio
Seon Joon Kim,†,¶ Hyeong-Jun Koh,†,¶ Chang E. Ren,‡ Ohmin Kwon,§ Kathleen Maleski,‡
Soo-Yeon Cho,† Babak Anasori,‡ Choong-Ki Kim,∥ Yang-Kyu Choi,∥ Jihan Kim,§,⊥ Yury Gogotsi,*,‡
and Hee-Tae Jung*,†,⊥
†
National Research Laboratory for Organic Optoelectronic Materials, Department of Chemical and Biomolecular Engineering (BK-21
Plus), §Department of Chemical and Biomolecular Engineering (BK-21 Plus), ∥School of Electrical Engineering, and ⊥KAIST
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Institute for Nanocentury, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Korea
‡
A.J. Drexel Nanomaterials Institute, Drexel University, Philadelphia, Pennsylvania 19104, United States
*
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S Supporting Information

ABSTRACT: Achieving high sensitivity in solid-state gas

sensors can allow the precise detection of chemical agents.
In particular, detection of volatile organic compounds
(VOCs) at the parts per billion (ppb) level is critical for
the early diagnosis of diseases. To obtain high sensitivity,
two requirements need to be simultaneously satisfied: (i)
low electrical noise and (ii) strong signal, which existing
sensor materials cannot meet. Here, we demonstrate that 2D
metal carbide MXenes, which possess high metallic
conductivity for low noise and a fully functionalized surface
for a strong signal, greatly outperform the sensitivity of conventional semiconductor channel materials. Ti3C2Tx MXene gas
sensors exhibited a very low limit of detection of 50−100 ppb for VOC gases at room temperature. Also, the extremely low
noise led to a signal-to-noise ratio 2 orders of magnitude higher than that of other 2D materials, surpassing the best sensors
known. Our results provide insight in utilizing highly functionalized metallic sensing channels for developing highly
sensitive sensors.
KEYWORDS: two-dimensional materials, MXene, titanium carbide, gas sensing, metallic channel, signal-to-noise ratio,
volatile organic compound

S ensitive gas detection is becoming increasingly important

in detecting toxic gases in air,1 pollution monitoring,2
and therapeutic diagnosis by breath analysis.3 In
particular, detection of volatile organic compounds (VOCs)
in exhaled breath below parts per million (ppm) level is critical
for the early diagnosis of illnesses.4 For example, the detection
of ammonia in the 50−2000 parts per billion (ppb) level is
highly required to diagnose peptic ulcers caused by Helicobacter
pylori infection or end-stage renal failure.5,6 Also, detection of
acetone at around the 300−1800 ppb level is required to
distinguish patients with diabetes from normal subjects.7,8
While sensitive detection has been easily achieved for highly
reactive gases such as H2S and NO2, it is a challenge to find
materials that can reliably detect ppb-level VOC gases, such as
acetone and ethanol, at room temperature. In order to obtain
very high sensitivity in typical resistive sensors, two require-
ments must be simultaneously satisfied: (i) low electrical noise
induced by high conductivity and (ii) high signal induced by
strong and abundant analyte adsorption sites. However, these
two features are always in a trade-off relation.
In order to achieve high sensitivity, a wide range of channel
materials has been employed for resistive sensors, which can be
mainly categorized into semiconducting and conducting
channels. Metal oxide semiconductors (MOS), in which the
atmosphere-dependent surface conductivity governs the
sensing mechanism, are representative semiconducting channel
materials. Although many reports show their high sensitivity,
MOS sensors only show both a high signal and low noise at
high temperatures due to the presence of an activation energy,
which is a critical limitation for portable devices. On the other
hand, highly conducting channel materials are likely to yield
low noise but lack gas adsorption sites required for a high
signal. Recently, two-dimensional (2D) materials9,10 such as
graphene,11 MoS2,12,13 and black phosphorus (BP)14 have
attracted interest due to their high surface area, versatile surface
chemistry, and capability of sensitive detection at room
temperature. Charge transfer from adsorbed molecules governs
Received: October 21, 2017
Accepted: January 5, 2018
Published: January 25, 2018

© 2018 American Chemical Society 986 DOI: 10.1021/acsnano.7b07460

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Figure 1. Schematic illustration of Ti3C2Tx films and their structural and surface characterizations. (a) Schematic illustration of the Ti3C2Tx
films and its atomic structure. (b) Scanning electron microscopy (SEM) image of the film surface, and a photographic image of a film sensor
(inset). The width of the substrate in the inset image is 1.5 cm. (c) I−V curves directly measured on the Ti3C2Tx film sensor via a two-terminal
method. (d−f) X-ray photoelectron spectra (XPS) of films after transfer at three core levels: (d) Ti 2p, (e) C 1s, (f) O 1s, and their
corresponding deconvoluted components. (g) Elemental mapping analyses of Ti3C2Tx films for Ti (yellow), C (green), O (red), and F
(purple).

the sensing mechanism in 2D materials, and similar trade-off
relations exist where low band gap materials such as graphene
suffer from a low signal. Various strategies have been employed
to increase the signal in these cases, such as introducing
abundant functional groups and defects, but these methods
greatly degrade electrical conductivity.15,16 On the other hand,
higher band gap materials such as MoS2 show a high signal, but
suffer from intrinsically high noise.
Here, we experimentally demonstrate Ti3C2Tx MXene film as
metallic channels for chemiresistive gas sensors with ultrahigh
sensitivity. MXenes are a large family of 2D transition metal
carbides/nitrides,17−19 where representative MXenes such as
Ti3C2(OH)2 possess metallic conductivity,20 while the outer
surface is fully covered with functional groups, showing that
metallic conductivity and abundant surface functionalities may
coexist without mutual interference.21 Such an interesting
combination renders them highly attractive for gas sensors with
a high signal-to-noise ratio (SNR), which indicates the relative
gas signal intensity over noise intensity, as the high coverage of
functional groups allow strong binding with analytes, while the
high metallic conductivity intrinsically leads to a low noise.
Also, several theoretical works have predicted the outstanding
properties of MXenes as gas sensors.22,23
RESULTS AND DISCUSSION
The schematic illustration of a fabricated Ti3C2Tx film sensor is
shown in Figure 1a. Ti3C2Tx was synthesized by etching Al
from Ti3AlC2 powders using the LiF/HCl route.17 In a typical
synthesis, resulting Ti3C2Tx flakes possess a highly conductive
Ti3C2 core and are fully terminated by hydroxyl (−OH) and
oxygen (−O) terminal groups on the surface, with fluorine
(−F) terminal groups also present. Ti3C2Tx films were
prepared by filtrating diluted colloidal solutions (Figure S1)
through an anodized aluminum oxide (AAO) membrane and
then transferred onto SiO2 wafers printed with gold-sensing
987
electrodes separated by 100 μm. Finally, fabricated Ti3C2Tx
sensors were inserted into a gas-sensing chamber, and the real-
time resistance variance data were acquired. Dynamic light
scattering (DLS) measurements using a diluted aqueous
solution revealed that the average particle size of Ti3C2Tx was
about 280 nm, in agreement with the observations of individual
delaminated flakes made by transmission electron microscopy
(TEM) (Figure S2). The scanning electron microscopy (SEM)
image in Figure 1b shows that these flakes were assembled into
a uniform film, displaying a flat surface without noticeable
defects. Atomic force microscopy (AFM) measurements
revealed a film thickness of ∼70 nm (Figure S3).
The good electrical conductivity was verified using two-
terminal I−V curve measurements, and abundant functional
groups were shown by X-ray photoelectron spectroscopy
(XPS) and elemental mapping by energy-dispersive X-ray
spectroscopy (EDX) in SEM. The linear I−V curve of a
Ti3C2Tx film in Figure 1c indicates Ohmic behavior,24 and the
calculated bulk conductivity of Ti3C2Tx films was 3250 S/m. A
conductivity lower than that of other reports may be due to
small flake size, which is required for gas uptake and transport
within the film, small thickness, and the large number of
interflake contact junctions. Then, XPS measurements were
performed on the Ti3C2Tx film sensors to determine the type
and relative amount of surface functionalities. The analysis was
conducted through peak fitting calculations using Gaussian−
Lorentzian curves. Figure 1d displays the Ti 2p core level fitted
with four doublets (Ti 2p1/2, Ti 2p3/2) with an area ratio of 1:2,
where each doublet is separated by 5.8 eV. The Ti 2p3/2
components at 454.6, 455.5, 456.7, and 458.5 eV were assigned
to Ti−C (Ti+), Ti−X (Ti2+), TixOy (Ti3+), and TiO2 (Ti4+),
respectively, where Ti−X corresponds to substoichiometric
titanium carbide or titanium oxycarbides.25 The TiO2 peak
slightly increased compared to the spectra of as-filtered Ti3C2Tx
films, suggesting that films might have been slightly oxidized
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Figure 2. Gas response performance of Ti3C2Tx sensors at room temperature. (a) Resistance variation and (b) maximal resistance change
upon exposure to 100 ppm of acetone, ethanol, ammonia, propanal, NO2, SO2, and 10000 ppm of CO2 at room temperature (25 °C). (c)
Resistance variation versus time upon exposure to highly diluted acetone (top), ethanol (middle), and ammonia (bottom) in ppb
concentration range (50−1000 ppb). (d) Maximal resistance change in a wide range of diluted target gases (0.05−1000 ppm). State-of-the-art
diagram of the limit of detection (LOD) for room temperature sensors based on 2D materials to detect (e) acetone and (f) ammonia, showing
Ti3C2Tx MXene has the smallest LOD. The Y-axes in (e) and (f) have no quantitative meaning; the lines were drawn at different heights of the
Y-axis only to spatially separate various families of 2D materials.

during the transfer process (Figure S4). The C 1s core level
(Figure 1e) was fitted with five components at 282.2, 284.6,
285.5, 287, and 289.1 eV, assigned to Ti−C, C−C, −CH2− and
−CH3, C−O, and −COO, respectively. For the O 1s core level
(Figure 1f), four components were fitted at 530.1, 530.6, 532.5,
and 533.8 eV, assigned to TiO2, substoichiometric TiOx, Ti−
OH, and adsorbed H2O on the surface,25 where the intensity of
the Ti−OH peak greatly increased after film transfer. These
results suggest that, in addition to surface contaminations and
oxidized regions, −OH terminal groups are present on the
surface of the Ti3C2Tx flakes. Furthermore, element analysis in
Figure 1g shows that surface elements (O, F) and core
elements (Ti, C) were evenly distributed across the entire film,
indicating that such surface functionalities were abundantly
present on the surface. Overall, these results indicate that
Ti3C2Tx films simultaneously possess a high conductivity with
abundant hydrophilic surface functionalities.
In order to investigate the gas-sensing performance of
Ti3C2Tx sensors, various gases were exposed to the Ti3C2Tx
films at room temperature. Figure 2a displays typical gas
responses of Ti3C2Tx sensors under exposure to 100 ppm of
acetone (CH3COCH3), ethanol (C2H5OH), ammonia (NH3),
propanal (C2H5CHO), nitrogen dioxide (NO2), sulfur dioxide
(SO2), and 10000 ppm of carbon dioxide (CO2), which were
diluted with N2 gas. The gas response was defined as the
relative change in the channel’s electrical resistance upon gas
injection compared to the baseline resistance (ΔR/Rb (%)).
Prior to the injection of target gases, Ti3C2Tx sensors were
exposed to pure N2 gas to stabilize the baseline resistance (Rb).
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Then, sensors were exposed to gases for 5 min, as indicated by
the shaded region, which was followed by the purging of N2 gas
for recovery to the baseline. Interestingly, Ti3C2Tx sensors
displayed a positive variation of resistance regardless of the type
of gases (oxidizing or reducing type), indicating that the charge
carrier transport of the channel was always hindered when a gas
molecule was adsorbed. Such a behavior has not been observed
in sensors based on semiconducting materials, in which the
response typically varies depending on the electron-donating/
accepting properties of analytes and the dominating charge
carrier type (p-, n-type) of the sensing channel.26,27 This
suggests that a different sensing mechanism is functioning, and
it is expected that the universal positive response of Ti3C2Tx is
due to its metallic conductivity,28 where gas adsorption reduces
the number of carriers, increasing the channel resistance.29
To further examine the selectivity of Ti3C2Tx channels, the
maximal response of each gas was measured and summarized in
Figure 2b. The gas response for acetone, ethanol, ammonia, and
propanal was 0.97, 1.7, 0.8, and 0.88%, respectively, with
ethanol showing the highest response, while the response for
NO2, SO2, and CO2 was significantly lower. The gas response
varied according to the thickness of Ti3C2Tx films (Figure S5),
which may be due to the different portion of total active sites
exposed to the surface. The results indicate that Ti3C2Tx
channels have a high selectivity toward gases capable of
hydrogen bonding over acidic gases, which is an interesting
behavior among channel materials for gas sensors. This
observation suggests that the terminal hydroxyl (−OH) groups
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Figure 3. Gas response and signal-to-noise ratio (SNR) of Ti3C2Tx sensors compared with sensors based on representative two-dimensional
materials. (a) Real-time gas response behavior of BP, MoS2, RGO, and Ti3C2Tx sensors to 100 ppm of target gases. (b) Maximal resistance
change of sensors upon exposure to 100 ppm of acetone, ethanol, ammonia, propanal, NO2, SO2, and 10000 ppm of CO2. Inset to the right
displays a magnified scale. (c) Electrical noise of sensors during N2 exposure. (d) Maximal SNR values of sensors upon exposure to 100 ppm
of acetone, ethanol, ammonia, and propanal. (e) Flicker noise measured by normalized noise power spectral density (SI/I2) as a function of
frequency.

on the surface of Ti3C2Tx may play an important role in the
detection of the target species.
To investigate the sensitivity and the limit of detection
(LOD) of Ti3C2Tx sensors toward VOCs, responses to gases at
ppb concentrations were measured, and Ti3C2Tx sensors
showed outstanding sensitivity at ppb levels. Figure 2c displays
the resistance variation of Ti3C2Tx in highly diluted acetone
(50−1000 ppb), ethanol (100−1000 ppb), and ammonia
(100−1000 ppb). Ti3C2Tx sensors displayed a high-resolution,
positive response at very low gas concentrations, and the
response gradually increased as the gas concentration was
increased to higher values. Furthermore, we investigated the
maximal gas responses of acetone, ethanol, and ammonia in a
wide range of concentrations from 50 ppb to 1000 ppm, as
shown in Figure 2d. The response toward ethanol gradually
increased according to gas concentration within the entire
range, while the response toward acetone and ammonia
displayed a saturating behavior at higher concentrations at
the ppm level, which can be attributed to the saturation of
active sites on the surface.30,31 It is noteworthy that our
Ti3C2Tx films represent the first 2D material gas sensors
capable of detecting various VOCs such as acetone and ethanol
under 100 ppb level with room temperature operation with no
pretreatment, which is a critical requisite for early therapeutic
diagnosis. Unlike gases such as H2S and NO2, which are easily
detectable at ppb levels due to high reactivity, the sensitive
detection of such VOC gases at ppb levels has been hard to
989
achieve. Figure 2e,f and Table S1 display the state-of-the-art
performance of 2D material-based gas sensors for acetone and
ammonia detection. The LOD of the Ti3C2Tx sensor is the
lowest among all types of sensors based on 2D materials, such
as transition metal dichalcogenides, graphene, and black
phosphorus (BP). To further estimate the achievable LOD of
Ti3C2Tx sensors, the SNR for highly diluted gases in the ppb
range was measured. SNR values were calculated by dividing
the gas response by the electrical noise. As shown in Figure S6
and Table S2, Ti3C2Tx sensors displayed significantly high SNR
values in the entire ppb range, and a SNR of 25.6 was achieved
for acetone detection at an extremely low concentration of 50
ppb. As the dilution system in our testing apparatus was limited
to 50 ppb, the theoretically achievable LOD (corresponding to
a SNR of 3)32 was derived using a power-law equation, which is
used to fit the response of channels with heterogeneous surface
functionalities at low gas concentrations.33 Calculations
revealed a sub-ppb level theoretical LOD for acetone and
ammonia, which were 0.011 and 0.13 ppb, respectively (Figure
S7). This is a value comparable to the best performing sensors
at room temperature such as Si NWs34 and Au nanoparticles.4
We also compared sensitivity of Ti3C2Tx sensors, with
sensors fabricated from representative 2D materials including
BP, MoS2, and reduced graphene oxide (RGO). Exfoliated
nanoflakes having similar size with Ti3C2Tx were used: 645 nm
(MoS2), 353 nm (BP), and 1228 nm (RGO) as measured by
DLS (Figure S8). Raman spectra of MoS2 sensors revealed peak
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Figure 4. Density functional theory (DFT) simulation results for gas molecules adsorbed on various 2D materials. Side and top views of the
minimum energy configurations for (a) acetone and (b) ammonia on Ti3C2(OH)2. (c) Minimum binding energies of acetone and ammonia
on Ti3C2(OH)2, Ti3C2O2, Ti3C2F2, graphene, MoS2, and BP.
positions at 377 (1E2g) and 402 cm−1 (A1g), and peaks of BP
sensors appeared at 360 (1Ag), 435 (B2g), and 463 cm−1 (2Ag).
In addition, representative peaks of RGO appeared at 1351 (D)
and 1603 cm−1 (G), indicating that all materials retained their
structure. Figure 3a shows the real-time gas response of BP,
MoS2, RGO, and Ti3C2Tx sensors under exposure to 100 ppm
of acetone, ethanol, and ammonia, and the maximal response of
each sensor to various gases employed in this study is displayed
in Figure 3b and Table S3. Sensors fabricated with semi-
conducting materials having a significant band gap (MoS2, BP)
displayed the highest response and high selectivity to ammonia.
On the other hand, sensors based on conducting materials
(RGO, Ti3C2Tx) displayed relatively low gas response, where
RGO did not display noticeable selectivity between exposed
gases. Such a low gas response reflects typical sensing behavior
observed in 2D materials, in which conductivity change is less
probable in small band gap semiconductors due to a high
carrier concentration.35 The higher response of Ti3C2Tx to
VOCs compared to that of RGO can be due to the abundant
functional groups on the surface. Also, only Ti3C2Tx showed a
positive response for both ammonia and NO2 (Figure S9), as
all other 2D materials are semiconductors or semimetals.35−37
Prior to calculating the SNR, the electrical noise of each
sensor was initially determined by measuring the average
resistance fluctuation during N2 introduction. Calculated noise
levels, as shown in Figure 3c, were approximately 1.5, 1.0, 0.02,
and 0.005% for BP, MoS2, RGO, and Ti3C2Tx, respectively,
where Ti3C2Tx displayed the lowest noise level. The low noise
of Ti3C2Tx may originate from its low electrical resistance
(Table S4), in which the structural uniformity of our vacuum-
filtrated films provides higher electrical conductivity toward a
lower LOD compared to Ti3C2Tx films fabricated by other
methods such as drop-casting.38 Based on the gas response and
noise of each 2D material above, we measured the SNR of each
sensor toward representative hydrogen-bonding gases. Figure
3d compares the SNR values of BP, MoS2, RGO, and Ti3C2Tx
sensors upon introduction of 100 ppm acetone, ethanol,
ammonia, and propanal. For acetone, ethanol, and propanal,
Ti3C2Tx displayed SNR of 236, 351, and 177, respectively,
which was 34, 33, and 54 times larger than that of the
maximum SNR value among other 2D materials. The SNR of
Ti3C2Tx also reached 160 for ammonia, which was 3.8 times
higher than that of BP. In addition, by observing the trend in
gas response and the SNR for various 2D materials, our results
directly show that a high sensor response to a specific gas does
not always lead to a high SNR. The overall SNR values are
displayed in Table S5, which shows that the SNR of Ti3C2Tx
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sensors is up to 2 orders of magnitude higher than those of
other 2D material-based sensors.
To understand the origin of the low electrical noise of
Ti3C2Tx sensors leading to a high SNR, we further investigated
the low-frequency noise of each material, which largely
contributes to overall noise when external current is applied
(1.5−3 V is applied for gas-sensing measurements). SI/I2
values39 of various 2D materials as a function of frequency
were compared, as shown in Figure 3e, where SI is the spectral
density of the gas sensor current and I is the average current
value. In the low-frequency range (<1 kHz), the SI/I2 of all
channels decreased as frequency increased with a slope of 1/f,
corresponding to the flicker (1/f) noise. Among channels, BP
displayed the highest noise density, followed by MoS2 and
RGO, while the spectral density of Ti3C2Tx was the lowest
among four channels. According to the Hooge formula, flicker
noise is inversely proportional to the electrical conductivity of a
material, which has also been observed in 2D systems.40 As the
intrinsic electrical conductivity of Ti3C2Tx is very high,41 it can
be concluded that the low electrical noise of the Ti3C2Tx sensor
originates from its excellent electrical conductivity. This result
suggests that metallic channels can provide an intrinsically
lower noise compared to semiconducting channels, which is
required for highly sensitive detection. However, the sensor
film should be uniform with good interflake contacts to take
advantage of the intrinsic conductivity of MXenes.
To investigate the mechanisms behind the superior
sensitivity of Ti3C2Tx films toward representative hydrogen-
bonding gases, density functional theory (DFT) simulations
were conducted to compute the binding energy of acetone and
ammonia on Ti3C2Tx, MoS2, graphene, and BP. For Ti3C2Tx, a
surface fully terminated with hydroxyl (−OH) groups
(Ti3C2(OH)2) was mainly investigated as they were predom-
inantly present in our film, and we assumed those groups to be
responsible for binding gas molecules (Ti3C2Tx with oxygen
(−O) groups (Ti3C2O2) and fluorine (−F) groups (Ti3C2F2)
were also investigated). DFT simulations elucidated the
molecular configurations with the strongest binding energies,
as shown in Figure 4a,b and Figure S10, while configurations
with weaker binding energy values are shown in Figures S11
and S12. The minimum binding energies of acetone on
Ti3C2(OH)2, Ti3C2O2, Ti3C2F2, graphene, MoS2, and BP
(Figure 4c) were −0.774, −0.317, −0.311, −0.367, −0.224, and
−0.328 eV, respectively, and the binding energies of ammonia
were −0.491, −0.355, −0.172, −0.132, −0.162, and −0.222 eV,
respectively (all of the gas-host DFT results are summarized in
Table S6). For both gases, Ti3C2(OH)2 displayed the strongest
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binding energy strengths that are more than twice that of any
other 2D materials, consistent with the extremely short vertical
equilibrium distance between the gas molecules and
Ti3C2(OH)2 (1.21 Å for acetone, 1.81 Å for ammonia). The
simulation results agree well with previously published studies
where hydroxyl-group-terminated MXene displayed stronger
gas adsorption compared to oxygen-group-terminated
MXene.22 We surmise that the superior gas adsorption
properties on the hydroxyl groups of Ti3C2Tx largely contribute
to the high sensitivity observed in our experimental data.
CONCLUSIONS
In summary, we have synthesized Ti3C2Tx chemical sensors
with superior gas-sensing properties over previously studied
materials. Ti3C2Tx sensors exhibited high selectivity toward
hydrogen-bonding gases over acidic gases, and the empirical
LOD of 50 ppb and the theoretical LOD in the sub-ppb level
for VOC gases are the lowest of any gas sensors based on 2D
materials operating at room temperature with no pretreatment.
Moreover, the SNR of Ti3C2Tx sensors was up to 2 orders of
magnitude higher compared to that of all other 2D materials.
Noise power spectral density measurements and DFT
calculations revealed that the excellent metallic conductivity
of the core channels and the strong adsorption energy of the
surface functional groups are both responsible for the extremely
high sensitivity of Ti3C2Tx sensors. As Ti3C2Tx is fully covered
with functional groups, selectivity toward certain gases may also
be controlled by ligand functionalization or defect engineering.
It is noteworthy that only one type of MXene (which may not
even be the best one) was studied here, but it already well
exceeded the performance of conventional materials. We expect
that this study will open the door for a large family of MXenes
to be employed as highly sensitive sensors.
METHODS
Synthesis of Ti3C2Tx. Ti3C2Tx was chosen out of many MXenes
due to a few reasons: (i) it is the most widely studied MXene; (ii) it
has a high electrical conductivity; and (iii) it is relatively stable in
various environments. Ti3C2Tx MXene was synthesized by selective
etching of Al from Ti3AlC2.17,42 Etching was done by adding 2 g of
lithium fluoride (LiF) to 20 mL of 9 M hydrochloric acid (HCl) while
stirring with a Teflon magnetic stir bar. Two grams of Ti3AlC2 was
added to the solution slowly, over the course of a few minutes. The
solution was stirred for 24 h at 35 °C. After the required etching time,
the mixture was washed with deionized water and centrifuged until the
pH reached ∼6. To obtain multilayered Ti3C2Tx, the solid residue was
redispersed with deionized water and vacuum-filtered over a porous
membrane (0.22 μm pore diameter, PVDF Durapore membrane). To
obtain a colloidal solution of delaminated Ti3C2Tx flakes, 400 mg of
multilayered Ti3C2Tx was added to 100 mL of deionized water and
sonicated for 1 h (Branson Ultrasonic Cleaner, 40 kHz) in an ice bath.
Then, the solution was centrifuged at 3500 rpm for 1 h, and the dark
supernatant was kept for further film fabrication.
Preparation of Black Phosphorus, MoS2, and Reduced
Graphene Oxide Solutions. For the preparation of a BP solution,
20 mg of bulk BP chunks (Smart Elements) was slightly ground by
mortar, and the ground BP was immersed in 50 mL of N-methyl-2-
pyrrolidone, which was then subjected to horn sonication (Vibracell
CVX, 750 W) for 5 h inside an ice bath to minimize solvent heating
and BP oxidation. After sonication, the dispersion was centrifuged at
5000 rpm for 30 min. The supernatant was used for fabricating thin
films. For the preparation of a MoS2 solution, MoS2 powders (Sigma-
Aldrich, <2 μm powder, 400 mg) were immersed in an ethanol/water
mixture (45% v/v), which was then subjected to bath sonication for 12
h while suppressing temperature increase. For the preparation of a
RGO powders, graphene oxide (GO) was synthesized by the modified
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Hummers’ method with natural graphite (Graphit Kropfmühl GmbH,
FP 99.5%). Then, GO was thermally reduced at 850 °C under Ar
environment to obtain fine RGO powders. RGO powder was
dispersed in ethanol and then subjected to bath sonication for 2 h.
For all solutions, non-exfoliated large particles were removed by
sedimentation, and only the supernatant was used for fabricating thin
films.
Ti3C2Tx, BP, MoS2, and RGO Film Fabrication and Transfer
onto a Sensor Electrode. Diluted solutions of Ti3C2Tx, BP, MoS2,
and RGO were subjected to vacuum filtration through a porous AAO
filter (200 nm pore diameter, Whatman) to form a thin film. Filtered
films on AAO were placed in a vacuum oven, which was increased to
60 °C in vacuum and dried for 1 h. After being dried, films on AAO
were floated on a 2 M NaOH aqueous solution to dissolve the alumina
membrane. While the films were floating on the surface, the NaOH
solution was replaced with distilled water and thoroughly washed by
recirculation until the pH was near 7. Then, the floating films were
carefully placed on a SiO2 wafer preprinted with Au electrodes by
slowly draining the water solution. Finally, transferred films on SiO2
were dried in a vacuum oven at 60 °C for 30 min to complete the
fabrication.
Gas Delivery System and Resistance Measurements. In order
to measure the dynamic resistance variation of sensors, a 5 nm thick
Cr adhesion layer and 65 nm thick Au electrodes were sequentially
deposited by electron beam evaporation through a customized hard
mask. The spacing between the electrodes was 100 μm. After channel
materials were transferred onto the preprinted electrodes, the prepared
sensors were mounted onto a homemade gas-sensing chamber where a
heating module below the sensing chamber maintained the reaction
chamber temperature at 25 °C. Target gases were diluted with N2, and
the flow rates were appropriately controlled by mass flow controllers
(Brooks, 5850E) to obtain desired gas concentrations. The resistance
signal of the mounted sensor was measured by a data acquisition
module (Agilent 34970A). The dilution system in our testing
apparatus was limited to 50 ppb for acetone and 100 ppb for ethanol
and ammonia, and analyses of gas responses below these
concentrations were not conducted.
Noise Power Spectral Density (PSD) Measurements. The
noise PSD was obtained by measuring anode current (Ianode)
fluctuation using a dynamic signal analyzer (Agilent 89410A) in
frequency domain. In the measurement, the anode voltage (Vanode) was
fixed to 1 V. Sensitivity values of the low noise preamplifier (SR570)
for sensors composed of Ti3C2Tx, RGO, BP, and MoS2 channels were
set to 500 μA/V, 500 μA/V, 10 μA/V, and 2 nA/V, respectively, in
order to obtain optimized amplitudes of the PSD. The measurement
was conducted in ambient air condition at room temperature.
Binding Energy Calculations via Density Functional Theo-
ries. Using the Vienna ab initio software package (VASP),43−45
density functional theory calculations were conducted to obtain
binding energy of the gas molecules adsorbed onto the 2D materials.
The electron−ion interactions of each atom were expressed by the
projector-augmented wave46 method. The generalized gradient
approximation of Perdew, Burke, and Ernzerhof47 was used to
calculate the exchange-correlational energy term, and Grimme’s D2
correction method48 was used to describe the van der Waals
interaction. A plane wave basis set with cutoff energy of 520 eV was
used with a force threshold of 0.01 eV/Å for the ionic relaxation. The
3 × 3 × 1 supercells of 2D materials were used for all of calculations,
and 4 × 4 × 1 Monkhorst−Pack k-point grids49 were adopted with a
vacuum layer with thickness of 20 Å.
To calculate binding energy between 2D materials and gas
molecules, several configurations of gas molecules were adopted (see
Supporting Information). The binding energy was calculated using the
following formula:
ΔE binding = E2D material + gas − (E2D material + Egas)
The structures of MoS2 and BP were obtained from crystallography
open database, and those of Ti3C2Tx and graphene were obtained from
other cited works.50,51
DOI: 10.1021/acsnano.7b07460
ACS Nano 2018, 12, 986−993
ACS Nano
Characterization. The surface morphology of films was observed
by scanning electron microscopy (FEI Magellan400, FEI Nova230)
and atomic force microscopy (Park Systems). Transmission electron
microscopy (FEI Tecnai G2 F30 S-Twin) was used to observe the
morphology of individual flakes. For TEM sample preparation, highly
diluted Ti3C2Tx aqueous solution was drop-casted on a holey carbon
Cu TEM grid, which was dried at room temperature. Dynamic light
scattering (Particle Sizing Systems Nicomp 380 submicron particle
sizer) was used to measure the size distribution of individual flakes
inside solutions. X-ray photoelectron spectroscopy (Thermo VG
Scientific Sigma Probe) and Raman spectroscopy (Horiba Jobin Yvon
Aramis, 514 nm laser) were used to further characterize the film
structure and chemical composition.
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsnano.7b07460.
Image of the Ti3C2Tx aqueous solutions, SEM, AFM
images, and XPS spectra of the Ti3C2Tx films, SEM
images, Raman spectra, and DLS analysis of BP, MoS2,
RGO, gas response and SNR of Ti3C2Tx, BP, MoS2,
RGO sensors, DFT calculations of binding energy (PDF)
AUTHOR INFORMATION
Corresponding Authors
*E-mail: gogotsi@drexel.edu.
*E-mail: heetae@kaist.ac.kr.
ORCID
Kathleen Maleski: 0000-0003-4032-7385
Babak Anasori: 0000-0002-1955-253X
Yang-Kyu Choi: 0000-0001-6678-5451
Yury Gogotsi: 0000-0001-9423-4032
Hee-Tae Jung: 0000-0002-5727-6732
Author Contributions
¶ 2016, 28, 7020−7028.
S.J.K. and H.-J.K. contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We thank Yong-Jae Kim for I−V measurements, and Sang Min
Lee of Prof. Shin-Hyun Kim’s group at KAIST for their help in
dynamic light scattering measurements. This research was
supported by the Ministry of Science, ICT, and Future
Planning (MSIP; 2015R1A2A1A05001844), and the Leading
Foreign Research Institute Recruitment Program funded by the
Korean National Research Foundation (NRF) via the NNFC-
KAIST-Drexel FIRST Nano2 Co-op Center
(2016K1A4A3945038, 2015K1A4A3047100). This research
used resources of the National Energy Research Scientific
Computing Center (NERSC), a DOE office of science user
facility supported by the Office of Science of the U.S.
Department of Energy under Contract No. DE-AC02-
05CH11231.
REFERENCES
(1) Utriainen, M.; Kärpänoja, E.; Paakkanen, H. Combining
Miniaturized Ion Mobility Spectrometer and Metal Oxide Gas Sensor
for the Fast Detection of Toxic Chemical Vapors. Sens. Actuators, B
2003, 93, 17−24.
(2) Wetchakun, K.; Samerjai, T.; Tamaekong, N.; Liewhiran, C.;
Siriwong, C.; Kruefu, V.; Wisitsoraat, A.; Tuantranont, A.;
Phanichphant, S. Semiconducting Metal Oxides as Sensors for
992
Article
Environmentally Hazardous Gases. Sens. Actuators, B 2011, 160,
580−591.
(3) Turner, A. P. F.; Magan, N. Electronic Noses and Disease
Diagnostics. Nat. Rev. Microbiol. 2004, 2, 161−166.
(4) Kahn, N.; Lavie, O.; Paz, M.; Segev, Y.; Haick, H. Dynamic
Nanoparticle-based Flexible Sensors: Diagnosis of Ovarian Carcinoma
from Exhaled Breath. Nano Lett. 2015, 15, 7023−7028.
(5) Kearney, D. J.; Hubbard, T.; Putnam, D. Breath Ammonia
Measurement in Helicobacter Pylori Infection. Dig. Dis. Sci. 2002, 47,
2523−2530.
(6) Timmer, B.; Olthuis, W.; Berg, A. v. d. Ammonia Sensors and
Their ApplicationsA Review. Sens. Actuators, B 2005, 107, 666−677.
(7) Kim, N.-H.; Choi, S.-J.; Kim, S.-J.; Cho, H.-J.; Jang, J.-S.; Koo, W.-
T.; Kim, M.; Kim, I.-D. Highly Sensitive and Selective Acetone Sensing
Performance of WO3 Nanofibers Functionalized by Rh2O3 Nano-
particles. Sens. Actuators, B 2016, 224, 185−192.
(8) Koo, W. T.; Yu, S.; Choi, S.-J.; Jang, J.-S.; Cheong, J. Y.; Kim, I.-
D. Nanoscale PdO Catalyst Functionalized Co3O4 Hollow Nanocages
Using MOF Templates for Selective Detection of Acetone Molecules
in Exhaled Breath. ACS Appl. Mater. Interfaces 2017, 9, 8201−8210.
(9) Liu, X.; Ma, T.; Pinna, N.; Zhang, J. Two-Dimensional
Nanostructured Materials for Gas Sensing. Adv. Funct. Mater. 2017,
27, 1702168.
(10) Yang, S.; Jiang, C.; Wei, S.-H. Gas Sensing in 2D materials. Appl.
Phys. Rev. 2017, 4, 021304.
(11) Wu, J.; Feng, S.; Wei, X.; Shen, J.; Lu, W.; Shi, H.; Tao, K.; Lu,
S.; Sun, T.; Yu, L.; Du, C.; Miao, J.; Norford, L. K. Facile Synthesis of
3D Graphene Flowers for Ultrasensitive and Highly Reversible Gas
Sensing. Adv. Funct. Mater. 2016, 26, 7462−7469.
(12) Kim, J. S.; Yoo, H. W.; Choi, H. O.; Jung, H.-T. Tunable
Volatile Organic Compounds Sensor by Using Thiolated Ligand
Conjugation on MoS2. Nano Lett. 2014, 14, 5941−5947.
(13) Cho, S.-Y.; Kim, S. J.; Lee, Y.; Kim, J.-S.; Jung, W.-B.; Yoo, H.-
W.; Kim, J.; Jung, H.-T. Highly Enhanced Gas Adsorption Properties
in Vertically Aligned MoS2 Layers. ACS Nano 2015, 9, 9314−9321.
(14) Cho, S.-Y.; Lee, Y.; Koh, H.-J.; Jung, H.; Kim, J.-S.; Yoo, H.-W.;
Kim, J.; Jung, H.-T. Superior Chemical Sensing Performance of Black
Phosphorus: Comparison With MoS2 and Graphene. Adv. Mater.
(15) Morimoto, N.; Kubo, T.; Nishina, Y. Tailoring the Oxygen
Content of Graphite and Reduced Graphene Oxide for Specific
Applications. Sci. Rep. 2016, 6, 21715.
(16) Wu, Z.; Luo, Z.; Shen, Y.; Zhao, W.; Wang, W.; Nan, H.; Guo,
X.; Sun, L.; Wang, X.; You, Y.; Ni, Z. Defects as a Factor Limiting
Carrier Mobility in WSe2: A Spectroscopic Investigation. Nano Res.
2016, 9, 3622−3631.
(17) Anasori, B.; Lukatskaya, M. R.; Gogotsi, Y. 2D Metal Carbides
and Nitrides (MXenes) for Energy Storage. Nat. Rev. Mater. 2017, 2,
16098.
(18) Zhu, M.; Huang, Y.; Deng, Q.; Zhou, J.; Pei, Z.; Xue, Q.; Huang,
Y.; Wang, Z.; Li, H.; Huang, Q.; Zhi, C. Highly Flexible, Freestanding
Supercapacitor Electrode With Enhanced Performance Obtained by
Hybridizing Polypyrrole Chains With MXene. Adv. Energy Mater.
2016, 6, 1600969.
(19) Xue, Q.; Zhang, H.; Zhu, M.; Pei, Z.; Li, H.; Wang, Z.; Huang,
Y.; Huang, Y.; Deng, Q.; Zhou, J.; Du, S.; Huang, Q.; Zhi, C.
Photoluminescent Ti3C2 MXene Quantum Dots for Multicolor
Cellular Imaging. Adv. Mater. 2017, 29, 1604847.
(20) Xie, Y.; Kent, P. R. C. Hybrid Density Functional Study of
Structural and Electronic Properties of Functionalized Tin+1Xn (X = C,
N) Monolayers. Phys. Rev. B: Condens. Matter Mater. Phys. 2013, 87,
235441.
(21) Shahzad, F.; Alhabeb, M.; Hatter, C. B.; Anasori, B.; Hong, S.
M.; Koo, C. M.; Gogotsi, Y. Electromagnetic Interference Shielding
With 2D Transition Metal Carbides (MXenes). Science 2016, 353,
1137−1140.
(22) Yu, X.-F.; Li, Y.-C.; Cheng, J.-B.; Liu, Z.-B.; Li, Q.-Z.; Li, W.-Z.;
Yang, X.; Xiao, B. Monolayer Ti2CO2: A Promising Candidate for NH3
DOI: 10.1021/acsnano.7b07460
ACS Nano 2018, 12, 986−993
ACS Nano Article

Sensor or Capturer With High Sensitivity and Selectivity. ACS Appl. (42) Ghidiu, M.; Lukatskaya, M. R.; Zhao, M. Q.; Gogotsi, Y.;
Mater. Interfaces 2015, 7, 13707−13713. Barsoum, M. W. Conductive Two-Dimensional Titanium Carbide
(23) Xiao, B.; Li, Y.-C.; Yu, X.-F.; Cheng, J.-B. MXenes: Reusable ’Clay’ With High Volumetric Capacitance. Nature 2014, 516, 78−81.
Materials for NH3 Sensor or Capturer by Controlling the Charge (43) Kresse, G.; Hafner, J. Ab initio Molecular Dynamics for Liquid
Injection. Sens. Actuators, B 2016, 235, 103−109. Metals. Phys. Rev. B: Condens. Matter Mater. Phys. 1993, 47, 558−561.
(24) Xu, B.; Zhu, M.; Zhang, W.; Zhen, X.; Pei, Z.; Xue, Q.; Zhi, C.; (44) Kresse, G.; Furthmüller, J. Efficiency of ab-initio Total Energy
Shi, P. Ultrathin MXene-Micropattern-Based Field-Effect Transistor Calculations for Metals and Semiconductors Using a Plane-Wave Basis
for Probing Neural Activity. Adv. Mater. 2016, 28, 3333−3339. Set. Comput. Mater. Sci. 1996, 6, 15−50.
(25) Halim, J.; Lukatskaya, M. R.; Cook, K. M.; Lu, J.; Smith, C. R.; (45) Kresse, G.; Furthmüller, J. Efficient Iterative Schemes for ab
Näslund, L.-Å.; May, S. J.; Hultman, L.; Gogotsi, Y.; Eklund, P.; initio Total-Energy Calculations Using a Plane-Wave Basis Set. Phys.
Barsoum, M. W. Transparent Conductive Two-Dimensional Titanium Rev. B: Condens. Matter Mater. Phys. 1996, 54, 11169−11186.
Carbide Epitaxial Thin Films. Chem. Mater. 2014, 26, 2374−2381. (46) Blöchl, P. E. Projector Augmented-Wave Method. Phys. Rev. B:
(26) Schedin, F.; Geim, A. K.; Morozov, S. V.; Hill, E. W.; Blake, P.; Condens. Matter Mater. Phys. 1994, 50, 17953−17979.
Katsnelson, M. I.; Novoselov, K. S. Detection of Individual Gas (47) Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient
Molecules Adsorbed on Graphene. Nat. Mater. 2007, 6, 652−655. Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 3865−3868.
(27) Mao, S.; Cui, S.; Lu, G.; Yu, K.; Wen, Z.; Chen, J. Tuning Gas- (48) Grimme, S. Semiempirical GGA-type Density Functional
sensing Properties of Reduced Graphene Oxide Using Tin Oxide Constructed With a Long-Range Dispersion Correction. J. Comput.
Nanocrystals. J. Mater. Chem. 2012, 22, 11009−11013. Chem. 2006, 27, 1787−1799.
(28) Anasori, B.; Shi, C.; Moon, E. J.; Xie, Y.; Voigt, C. A.; Kent, P. R. (49) Monkhorst, H. J.; Pack, J. D. Special Points for Brillouin-Zone
C.; May, S. J.; Billinge, S. J. L.; Barsoum, M. W.; Gogotsi, Y. Control of Integrations. Phys. Rev. B 1976, 13, 5188−5192.
(50) Khazaei, M.; Arai, M.; Sasaki, T.; Chung, C.-Y.;
Electronic Properties of 2D Carbides (MXenes) by Manipulating
Venkataramanan, N. S.; Estili, M.; Sakka, Y.; Kawazoe, Y. Novel
Their Transition Metal Layers. Nanoscale Horiz. 2016, 1, 227−234.
Electronic and Magnetic Properties of Two-Dimensional Transition
(29) An, K. H.; Jeong, S. Y.; Hwang, H. R.; Lee, Y. H. Enhanced
Metal Carbides and Nitrides. Adv. Funct. Mater. 2013, 23, 2185−2192.
Sensitivity of a Gas Sensor Incorporating Single-Walled Carbon
(51) Luo, X.; Lu, X.; Cong, C.; Yu, T.; Xiong, Q.; Quek, S. Y.
Nanotube−Polypyrrole Nanocomposites. Adv. Mater. 2004, 16, 1005− Stacking Sequence Determines Raman Intensities of Observed
1009. Interlayer Shear Modes in 2D Layered Materials-A General Bond
(30) Snow, E. S.; Perkins, F. K.; Robinson, J. A. Chemical Vapor Polarizability Model. Sci. Rep. 2015, 5, 14565.
Detection Using Single-Walled Carbon Nanotubes. Chem. Soc. Rev.
2006, 35, 790−798.
(31) Guo, Y.; Gong, M.; Li, Y.; Liu, Y.; Dou, X. Sensitive, Selective,
and Fast Detection of ppb-Level H2S Gas Boosted by ZnO-CuO
Mesocrystal. Nanoscale Res. Lett. 2016, 11, 475.
(32) Currie, L. A. Nomenclature in Evaluation of Analytical Methods
Including Detection and Quantification Capabilities. Pure Appl. Chem.
1995, 67, 1699−1723.
(33) Hu, N.; Yang, Z.; Wang, Y.; Zhang, L.; Wang, Y.; Huang, X.;
Wei, H.; Wei, L.; Zhang, Y. Ultrafast and Sensitive Room Temperature
NH3 Gas Sensors Based on Chemically Reduced Graphene Oxide.
Nanotechnology 2014, 25, 025502.
(34) Shehada, N.; Cancilla, J. C.; Torrecilla, J. S.; Pariente, E. S.;
Brönstrup, G.; Christiansen, S.; Johnson, D. W.; Leja, M.; Davies, M.
P. A.; Liran, O.; Peled, N.; Haick, H. Silicon Nanowire Sensors Enable
Diagnosis of Patients via Exhaled Breath. ACS Nano 2016, 10, 7047−
7057.
(35) Cui, S.; Pu, H.; Wells, S. A.; Wen, Z.; Mao, S.; Chang, J.;
Hersam, M. C.; Chen, J. Ultrahigh Sensitivity and Layer-Dependent
Sensing Performance of Phosphorene-Based Gas Sensors. Nat.
Commun. 2015, 6, 8632.
(36) Ohta, T.; Bostwick, A.; Seyller, T.; Horn, K.; Rotenberg, E.
Controlling the Electronic Structure of Bilayer Graphene. Science
2006, 313, 951−954.
(37) Radisavljevic, B.; Radenovic, A.; Brivio, J.; Giacometti, V.; Kis, A.
Single-Layer MoS2 Transistors. Nat. Nanotechnol. 2011, 6, 147−150.
(38) Lee, E.; VahidMohammadi, A.; Prorok, B. C.; Yoon, Y. S.;
Beidaghi, M.; Kim, D.-J. Room Temperature Gas Sensing of Two-
Dimensional Titanium Carbide (MXene). ACS Appl. Mater. Interfaces
2017, 9, 37184−37190.
(39) Bang, T.; Lee, B.-H.; Kim, C.-K.; Ahn, D.-C.; Jeon, S.-B.; Kang,
M.-H.; Oh, J.-S.; Choi, Y.-K. Low-Frequency Noise Characteristics in
SONOS Flash Memory With Vertically Stacked Nanowire FETs. IEEE
Electron Device Lett. 2017, 38, 40−43.
(40) Robinson, J. T.; Perkins, F. K.; Snow, E. S.; Wei, Z.; Sheehan, P.
E. Reduced Graphene Oxide Molecular Sensors. Nano Lett. 2008, 8,
3137−3140.
(41) Lipatov, A.; Alhabeb, M.; Lukatskaya, M. R.; Boson, a.; Gogotsi,
Y.; Sinitskii, A. Effect of Synthesis on Quality, Electronic Properties
and Environmental Stability of Individual Monolayer Ti3C2 MXene
Flakes. Adv. Electron. Mater. 2016, 2, 1600255.

993 DOI: 10.1021/acsnano.7b07460

ACS Nano 2018, 12, 986−993