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Exfoliated black phosphorus gas sensing properties at room temperature

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2016 2D Mater. 3 025002
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2D Mater. 3 (2016) 025002

doi:10.1088/2053-1583/3/2/025002

PAPER

RECEIVED

30 October 2015

Exfoliated black phosphorus gas sensing properties at room

temperature

REVISED

24 January 2016
ACCEPTED FOR PUBLICATION

M Donarelli1,4, L Ottaviano1,2, L Giancaterini3, G Fioravanti1, F Perrozzi1 and C Cantalini3

3 March 2016

PUBLISHED

30 March 2016

2
3
4

Department of Physical and Chemical Sciences, University of LAquila, Via Vetoio 10, 67100 LAquila, Italy
CNR-SPIN, UOS LAquila, Via Vetoio 10, 67100 LAquila, Italy
Department of Industrial and Information Engineering and Economics, University of LAquila, Via Gronchi 18, 67100 LAquila, Italy
Present address: Sensor Lab., Department of Information Engineering, University of Brescia & CNR-INO Brescia, Via Branze 38, 25123
Brescia, Italy.

E-mail: maurizio.donarelli@unibs.it
Keywords: black phosphorus, gas sensing, XPS, NO2, H2, NH3
Supplementary material for this article is available online

Abstract
Room temperature gas sensing properties of chemically exfoliated black phosphorus (BP) to oxidizing
(NO2, CO2) and reducing (NH3, H2, CO) gases in a dry air carrier have been reported. To study the gas
sensing properties of BP, chemically exfoliated BP akes have been drop casted on Si3N4 substrates
provided with Pt comb-type interdigitated electrodes in N2 atmosphere. Scanning electron
microscopy and x-ray photoelectron spectroscopy characterizations show respectively the occurrence
of a mixed structure, composed of BP coarse aggregates dispersed on BP exfoliated few layer akes
bridging the electrodes, and a clear 2p doublet belonging to BP, which excludes the occurrence of
surface oxidation. Room temperature electrical tests in dry air show a p-type response of multilayer BP
with measured detection limits of 20 ppb and 10 ppm to NO2 and NH3 respectively. No response to
CO and CO2 has been detected, while a slight but steady sensitivity to H2 has been recorded. The
reported results conrm, on an experimental basis, what was previously theoretically predicted,
demonstrating the promising sensing properties of exfoliated BP.

Introduction
After the discovery of graphene [1], great efforts have
been spent in the preparation and investigation of
single and few layered 2D functional materials suitable
for a wide, yet unexploited, range of applications.
Graphene, due to its intrinsically high surface to
volume ratio, has acquired tremendous interest for gas
sensing applications [2] and it can overcome some
typical drawbacks occurring in the common and
traditional metal oxide (MOX) gas sensors. Solid
aggregates of nanoparticles forming on the MOX
surface can inhibit sensitivity of the sensors to the
target gases [3]. Novel architectures, like hierarchical
and hollow MOX have been proposed to increase
surface to volume ratio of the sensing material.
However, their fabrication is hard and scarcely compatible with the industry needs of low cost and low
power consumption devices. 2D atomically thin
materials, having all their atoms exposed to the target
2016 IOP Publishing Ltd

gas molecules, represent an alternative option for a

new generation of gas sensors. In addition to the above
cited graphene, a large variety of 2D and quasi-2D
structures have been investigated in the last few years,
and many authors have suggested to use them for gas
sensing applications. Graphene oxide (GO) and
reduced GO have been demonstrated to be promising
materials to detect relative humidity (RH) [4] and
various gases [514]. Mono and few layer MoS2 and
other transition metal dichalcogenides sensing properties have also been investigated [1517]. The discovery and isolation of single layer black phosphorus
(BP) have opened new perspectives on the use of 2D
materials in gas sensing applications, also due to its
direct bandgap and its p-type nature [18]. Multi-layer
BP has been used to fabricate a eld effect transistor
[19, 20] and few ppb detection limit in argon [20] and
in dry air atmosphere [21] and at room temperature
(RT) has been reported to NO2. Exfoliated BP akes
have been reported also for ion [22] and humidity [23]

2D Mater. 3 (2016) 025002

M Donarelli et al

Figure 1. SEM images of the BP akes bridging two Pt electrodes (light gray) pre-patterned on the Si3N4 substrate (dark gray), acquired
at lower (main image) and higher (left inset) magnication. The scale bar (black line) in the left inset is 500 nm. Both images are
formed recording secondary electrons with an in-lens detector (accelerating voltage 5 kV). Right inset: schematic representation of the
device used for gas sensing tests.

sensing. Theoretical studies have been conducted on

the sensing performances of monolayer BP. Kou et al
[24] have studied the adsorption of several gas
molecules on monolayer BP using rst-principles
calculations, predicting BP sensing performances
higher than the MoS2 ones and following the sequence:
NO>NO2>NH3>CO2>CO (i.e. the best performances for NO detection, the worst for CO).
In this paper, we report the gas sensing properties
and morphological and structural characterizations of
chemically exfoliated BP akes at room temperature
(RT). The exfoliated BP akes have been exposed to
NO2, NH3, H2, CO2 and CO target gases, at RT, in a
dry air environment. BP akes detect NO2, NH3 and
H2, while they are insensitive to CO2 and CO.

Experimental
To obtain exfoliated BP akes, a procedure similar to
the one reported for other layered materials [25] has
been followed. 20 mg of high purity (99.99%) BP
crystal pieces (Smart-elements, GmbH) have been
dispersed in 4 ml of anhydrous N-methylpyrrolidone
(NMP, Sigma-Aldrich). The dispersion has been
sonicated for 5 h by an ultrasonic equipment
(UP100H) controlled at 25 C, set at 100 W and
30 kHz. To avoid BP degradation due to solvated H2O
[19], the sonication process has been performed in a
glow box, under N2 controlled atmosphere
(T=29.2 C, RH=(4.52)%).
BP samples have been fabricated in the same glow
box under N2 atmosphere by dropping 20 l of the as
prepared solution on both 100 nm thick Au/Si (100)
and Si3N4 substrates. The last ones have been pre-patterned with 30 m spaced interdigitated Pt-electrodes
(30 m wide). All the samples have been stabilized
2

under N2 at 75 C for 3 h, before structural and electrical characterizations. BP akes deposited on Au/Si
(100) substrate have been readily introduced in an
ultra-high vacuum chamber (UHV, base pressure
1010 Torr) to be characterized by x-ray photoelectron
spectroscopy (XPS). The XPS system is equipped with
a monochromatic Al K source (h=1486.6 eV) and
a PHI 1257 spectrometer (resolution 100 meV).
Microstructural analysis and electrical resistance
measurements have been performed on BP akes
deposited on Si3N4 pre-patterned substrates. A ZeissGemini LEO 1530 scanning electron microscope
(SEM) has been used for microstructural analysis.
Electrical resistance measurements have been performed at RT ((232) C) by exposing the exfoliated
BP akes to certied mixtures of NO2, CO2, H2, NH3,
CO diluted in dry air. These samples have been placed
inside a Teon chamber (500 cm3), provided with
Teon tubings, and they have been electrically characterized by a volt-amperometric technique for a period of one month, under owing gas mixtures
(500 sccm). Dry air conditioning (250 sccm) has been
maintained between test runs to avoid sample contamination. Teon tubings and chambers have been
used (instead of metallic ones) to obtain NO2 concentration values of the order of tens ppb, considering
that NO2 molecules tend to adsorb and react with
metallic surfaces. NO2 gas concentrations in the
downstream have been measured by means of Ansyco
AS32 M chemiluminescence analyzer (Environment
S A).

Results and discussion

The SEM images reported in gure 1 show several BP
akes deposited by drop casting on the Si3N4 substrate.

2D Mater. 3 (2016) 025002

M Donarelli et al

Figure 2. XPS P 2p (a) and O 1s (b) core level spectra of chemically exfoliated BP. Dark gray curves: experimental data; light gray lines:
tting curves; black lines: tting curves sum. Shirley backgrounds have been subtracted from the experimental data and are not
shown.

Dark regions are the Si3N4 substrate, lighter areas are

the Pt electrodes. SEM analysis reveals the presence of
BP coarse particles with exfoliated BP akes. The
deposited BP partially covered the substrate, due to the
deposition technique used (i.e. drop casting) and to
the low BP concentration in the solution. However,
the connection between adjacent Pt electrodes is
guaranteed thanks to the formation of a patchwork of
the deposited akes. This patchwork architecture
implies the formation of a large number of junctions
and percolating paths, which affect the baseline
resistance of the sample, but, as discussed later on, not
its gas sensing performances. Furthermore, the BP
ake size ranges from hundreds of nm to tens of m.
The akes dimensions can be ascribed to the chemical
exfoliation procedure.
The XPS core level spectra (P 2p and O 1s) of the
exfoliated BP deposited on Au/Si (100) have been
reported in gure 2. The acquired XPS spectra have
been aligned to the 4f7/2 core level peak of the Au substrate (84.0 eV). Dark gray lines are the experimental
data, which have been tted with Voigt line shapes
(light gray lines) and Shirley backgrounds (subtracted
to the spectra and not shown). The black curves in
gure 2 are the sum of the tting curves. The P 2p core
level spectrum (panel (a)) shows two peaks related to
the phosphorus 2p doublet, at binding energies of
130.1 eV and 130.9 eV, for 2p3/2 and 2p1/2 respectively, with full widths at half maximum (FWHMs) of
0.6 eV. The ratio between the 2p3/2 and 2p1/2 areas of
the tting curves has been set equal to 2. The binding
energies and FWHMs are in good agreement with the
literature [26, 27]. No spectral features have been
detected in the 132135 eV binding energies range,
where P 2p signal of POx species is usually recorded
[26]. The reported P 2p core level XPS spectrum indicates that the BP surface has not been oxidized during
the exfoliation process. The O 1s spectrum reported in
gure 2(b) conrms this conclusion. The O 1s spectrum has been tted with two Voigt line shapes. The
3

component 1 (2) is located at a binding energy of

532.7 eV (530.9 eV) and shows a FWHM of 2.0 eV
(1.3 eV). The component 1 broadening and binding
energy suggests that it is related to the oxygen of adsorbed water and/or hydrocarbon molecules [28, 29].
The adsorption of unwanted molecules on the BP surface and on the Au substrate probably occurred during
the sample transfer from the glow box used for the
exfoliation to the XPS UHV chamber. The component
2 binding energy is in good agreement with the one
reported for SnIxOy, which is a residual product of the
synthesis of BP crystal pieces [29].
To study the exfoliated BP gas sensing properties,
electrical tests have been carried out at RT
((232) C). Exfoliated BP akes deposited on Si3N4
prepatterned substrates have been exposed to oxidizing (NO2, CO2) and reducing (NH3, H2, CO) gases,
diluted in a dry air carrier. Dry air has been used both
to dilute the gas mixtures and to avoid the surface
degradation of BP akes, recently reported in moist
atmosphere [19, 30].
Figure 3 shows the RT gas responses of exfoliated
BP to increasing concentrations of NH3, H2 and NO2
in dry air, in terms of the electrical resistance of the
fabricated device. The rectangle heights represent the
target gas concentrations. Each detection step consists
of 60 min exposure to dry air, 60 min to target gas and
dry air, and again 60 min to dry air (which is part of the
subsequent step). The BP akes electrical resistance
curves under CO2 (1% vol.) and CO (100 ppm) exposures do not show any features and have not been
reported, suggesting that the BP akes cannot detect
the presence of these gases in dry air. The BP akes
resistance increases when exposed to reducing gases
(panel (a)), namely H2 and NH3, while it decreases
when exposed to NO2 (panel (b)), which is an oxidizing gas. Considering that, and the electron donor
(NH3, H2) and acceptor (NO2) natures of the target
gases, exfoliated BP akes show a typical p-type
response.

2D Mater. 3 (2016) 025002

M Donarelli et al

Figure 3. Room temperature dynamic gas responses to oxidizing and reducing gases in dry air carrier gas, reported in terms of the
device electrical resistance. (a) Response to reducing gases: NH3 (blue line) and H2 (black line), (b) response to the oxidizing gas NO2
(red line). The rectangle heights represent the target gases concentrations. The dotted lines represent the base line recovery plots
(dened in the main text).

The resistance value of the device before each sensing test is about 15 k. This suggests that the BPbased device recovers its original characteristics after
each sensing test and a few hours of stabilization in dry
air. The dotted lines in gure 3 represent the base line
recovery (BLR) plots, approximately showing the
trend of the resistance values before each target gas
insertion. BLR is dened as the sensing materials ability to recover its original resistance in air, after the target gas is switched off. The dotted lines slope is positive
when BP is exposed to NH3, while it remains almost
zero when exposed to NO2 and H2. The incomplete
recovery of the base line in air after gas exposure has
been previously investigated for graphene. In that case,
the existence of irreversible sites where target gas
molecules may strongly bind, physically represented
by defects, inhibits a complete desorption in the time
scale of a sensing cycle [31]. Furthermore, the slow and
incomplete recovery of the base line of few layers sensing materials after NH3 is switched off, has been
observed also for few layers reduced graphene oxide
[9] (in that case, authors showed that the recovery of
the base line is much faster after NO2 switching off
than NH3) and, recently, for few layer phosphorene, in
N2 environment [32]. To facilitate the desorption of
adsorbed gas molecules, usually the sensing material is
annealed at temperatures of hundreds C, while the BP
gas sensing tests reported in gures 3 and 4 have been
performed at RT. Very likely, the desorption mechanism depends on the binding strength of the adsorbed molecules on BP. Theoretical models discussing
the adsorption of a single gas molecule on a 55
phosphorene atomic supercell [24] have shown that
the binding strength is highly dependent on the
amount of the charge transfer between gas molecules
4

and BP. The binding energies decrease from NO to CO

and
follow
the
sequence:
NO>NO2>NH3>CO2>CO. Following the
binding energies trend, a faster and more effective desorption of NH3, in comparison to the NO2 desorption
is expected. The here reported experiments show that
the NH3 desorption from BP akes is slower and less
effective than the one for NO2. A tentative explanation
of this discrepancy is that exfoliated BP akes display a
more complicated structure than the single layer phosphorene investigated in [24]. Few layer BP can be considered as a porous body, formed by stacked 2D layers,
with 5 interlayer distance. For this reason, the desorption process can be controlled either by the surface
desorption (related to the binding energies reported in
[24]) and/or by the desorption of the molecules previously diffused between the BP layers. It is reasonable
to assume that the surface desorption is the fastest process, being related just to the charge transfer. Therefore, it is very likely that the NH3 slow desorption rate
is mainly dependent on the diffusion phenomena
inside the exfoliated BP: during the exposure step, the
NH3 molecules tend to diffuse between the BP layers
and the interlayer desorption results are slower than
the one from the exposed akes surface. This behavior
is similar to the one reported for packed graphene
sheets [33], regarding the onset of limiting gas diffusion conditions between the layers.
Exposing the devices to visible light enhances the
gas desorption from the 2D single layer, as demonstrated for graphene and MoS2 [34, 35]. The BP akes
have been exposed to visible light (=670 nm,
=550 nm, =430 nm) but no improvements of
the base line recovery have been achieved. This corroborates the thesis of the occurrence of gas diffusion in

2D Mater. 3 (2016) 025002

M Donarelli et al

Figure 4. Room temperature log-log plots of the RR (Rg/Ra) to oxidizing (NO2) and reducing (NH3 and H2) gases versus gas
concentrations. Dashed lines are the theoretical extrapolated curves.

BP akes, providing an evidence of the stacked nature

of the exfoliated BP.
In the gas sensing tests, relative response (RR) is
dened as the ratio Rg/Ra, where Rg (Ra) is the BP
resistance measured during target gas (dry air) exposure. RR values represent the BP akes ability to detect
a target gas, at a given concentration. The relative
responses account for the akes dimensions distribution, so they do not sensibly vary from one sample to
another. The log-log plots shown in gure 4 display
the BP exfoliated akes RR to oxidizing (NO2) and
reducing (NH3 and H2) gases versus gas concentrations. For each detected gas, log(RR) versus log (gas
concentration) shows a linear trend.
The lowest gas concentrations to which the BP
akes have been exposed are 20 ppb NO2, 10 ppm
NH3 and 5 ppm H2, with a signal to noise ratio (SNR)
of 5.2 (20 ppb NO2) and 4.8 (10 ppm NH3). SNR less
than the 3.0, i.e. below the commonly accepted threshold, has been calculated in correspondence to 5 ppm
H2. The lowest detected NO2 concentration is fully
consistent with the detection limit reported in a previous work [21], where a mechanically exfoliated BP
ake has been used for gas sensing. Indeed, the chemical exfoliation procedure allows the formation of exfoliated BP akes with a broad thickness range, from few
to hundreds nm. So, both few layers and bulkier BP
akes respond to NO2 concentrations, in the here
reported wide range of 20 ppb1 ppm. Theoretical
detection limits of 7 ppb NO2, about 80 ppb H2 and
1 ppm NH3 can be extrapolated from the experimental data (the dashed red, blue and black lines in
gure 4 are the extrapolation curves). Considering that
the lowest investigated concentrations are 20 ppb NO2
and 10 ppm NH3 and the extrapolated detection limits
are 7 ppb and 1 ppm respectively, it turns out that BP
akes are more sensitive to oxidizing gases with
respect to reducing ones. These characteristics and the
BP akes unchanged resistance values when exposed
to CO and CO2, are in good agreement with the
5

theoretically predicted superior attitude of NO2 to

lead to a higher charge transfer with respect to NH3,
CO2 and CO [20]. To the best of our knowledge,
hydrogen and ammonia responses, reported in
gures 3 and 4, black lines, are the rst experimental
evidences of the exfoliated BP gas sensing response to
ppm concentrations of H2 and NH3 at RT and in a dry
air environment. From XPS investigations, there is no
evidence of nitrogen in the BP akes (XPS survey,
gure S1, supplementary data), so the solvent used for
the chemical exfoliation is no more present in the BP
akes, and it does not play an active role in the gas sensing tests. Moreover, no chemical changes in exfoliated BP akes are detected (core level XPS spectra,
gure 2). Consistent with the XPS data, the exfoliated
BP akes ability to detect these target gases can be very
likely ascribed to the morphology of the akes themselves, with a large number of edges, which favors the
gas sensing. Furthermore, it is demonstrated that chemically exfoliated BP akes can achieve NO2 sensing
performances similar to the ones reported by Cui et al
[21] for a mechanically exfoliated BP ake. This fact
paves the way for the use of chemically exfoliated BP
akes for gas sensing applications, avoiding the use of
a time-consuming technique for the exfoliation and
for the fabrication of the metallic contacts, like electron beam lithography, focused ion beam lithography, etc.

Conclusions
The gas sensing properties and performances of
chemically exfoliated black phosphorus at RT have
been investigated. BP exfoliated akes have been drop
casted on a standard interdigitated substrate and the
samples have been annealed at 75 C in inert N2
atmosphere to avoid degradation of the akes. BP
akes have shown a p-type response at RT and in a dry
air environment, and they are sensitive to the lowest

2D Mater. 3 (2016) 025002

M Donarelli et al

NO2 and NH3 tested concentrations (20 ppb for NO2

and 10 ppm for NH3), with extrapolated theoretical
detection limits of 7 ppb and 1 ppm, respectively.
Furthermore, exfoliated BPs ability to detect H2 and
NH3 at few ppm in dry air at RT has been reported for
the rst time. A good recovery of the base line has been
reported after NO2 and H2 have been switched off. A
tentative explanation of the gas sensing mechanism
has been proposed, based on the binding energies of
the adsorbed gas molecules and on the morphology of
the BP exfoliated akes. Finally, BP akes do not show
any response to CO and CO2. The reported results
conrm what was previously theoretically predicted,
showing the promising gas sensing properties of
exfoliated BP akes and their capability to detect target
gases at RT.

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