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Individual gas sensor detecting dual exhaled

Cite this: J. Mater. Chem. A, 2020, 8,
biomarkers via a temperature modulated n/p
26004 semiconducting transition†
Xiaxia Xing,a Lingling Du,a Dongliang Feng,a Chen Wang,a Mingshui Yao,b
Xiaohu Huang,c Shixi Zhangd and Dachi Yang *a

Received 22nd September 2020
Accepted 13th November 2020
DOI: 10.1039/d0ta09321a
rsc.li/materials-a
The newly-emerged breath sensing detection of disease biomarkers (e.g., H2S and acetone) offers rapid and
noninvasive early diagnosis of diseases (e.g., halitosis and diabetes). Utilizing a single sensor to monitor dual
biomarkers may contribute to both miniaturized size and multi-detection if implemented, but remains
challenging. Here, interconnected BiFeO3/Bi25FeO40 nanoparticles (NPs,
22.5 nm in diameter)
synthesized via combined microwave hydrothermal and annealing methods have been developed to
selectively detect dual biomarkers of halitosis and diabetes. The selective detection has been modulated
by an n/p semiconducting transformation, and has been experimentally observed and theoretically
interpreted, in which electron–hole pairs are modulated due to the synergistic effect of temperature-
dependent adsorbed oxygen molecules and semiconducting band bending. Remarkably, the sensor
prototypes enable the selective detection of both H2S (n-type mode) and acetone (p-type mode)
biomarkers with superior stability and a ppb-level detection limit. Furthermore, practical human breath
has been experimentally simulated. Critically, the sensors with a waterproof membrane have been tested
by immersing them into water. Our strategy of the detection of dual exhaled biomarkers by a single gas
sensor may contribute to the integration and miniaturization of sensors, for upcoming intelligent medical
treatment.

Additionally, to achieve multi-detection and miniaturization,

1. Introduction
Exhaled biomarker analysis provides a feasible route towards
early diagnosis of serious diseases such as lung cancer, gastric
cancer and diabetes,1–4 and is thus of great potential in the
upcoming intelligent medical treatment eld.5 Traditionally,
the analysis of biomarkers requires complicated procedures,
time consumption, expensive facilities and procient exper-
tise.6–8 Currently, gas-sensing detection of human breath offers
rapid, inexpensive and non-invasive early-diagnosis.4,9 Gener-
ally, such gas sensors in the detection of biomarkers are
simultaneously endowed with excellent selectivity, stability and
ppb-level detection. Although progress has been made, devel-
oping such advanced sensors remains challenging.
a
Tianjin Key Laboratory of Optoelectronic Sensor and Sensing Network Technology,
Department of Electronics, College of Electronic Information and Optical
Engineering, Nankai University, Tianjin 300350, China. E-mail: yangdachi@nankai.
edu.cn
b
Institute for Integrated Cell-Material Sciences, Kyoto University Institute for Advanced
Study, Kyoto University, Yoshida Ushinomiya-cho, Sakyo-ku, Kyoto 606-8501, Japan
c
Institute of Materials Research and Engineering, Agency for Science, Technology and
Research, 138634, Singapore
d
Shangqiu Municipal Hospital, Shangqiu, 476100, China
† Electronic supplementary information (ESI) available. See
10.1039/d0ta09321a
the challenging issue is utilizing a single gas sensor to selec-
tively monitor two or more exhaled biomarkers.
To address such issues of sensing performance, the inte-
grated sensing materials, such as semiconductor metal oxides
(SMOs), play crucial roles and are hence widely studied. Basi-
cally, the SMO sensing mechanism is determined by the resis-
tance, in which the target gases are adsorbed onto and nally
vary the carrier concentration of the SMO. To improve the
selectivity, the approaches of doping precious metals,10,11 con-
structing a catalytically active overlayer12–14 and exploiting the
interaction between the target gas and sensing-material
surface15,16 have been explored. For improving the stability,
the methods of gas ltration,17 assembling moisture-resistant
materials18,19 and applying core/shell nanostructures20,21 have
been reported. To enable ppb-level detection, decorating
precious metals,22 constructing heterojunctions23 and light
assistance24–26 have been frequently utilized.
Recently, the behavior of an n/p semiconducting transition
in SMO sensing materials has been discovered under gas-
sensing environments, which can notably be modulated by
factors such as temperature,27,28 doping concentration,29 and
target gas concentration.30 Essentially, such transition behav-
DOI:
iors under interaction with the target gas are determined by
semiconducting materials, including pure SMOs,31–33 metallic-

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Fig. 1 The morphological and crystalline characterization of BiFeO3/Bi25FeO40 NPs. (a) SEM image. (b and f) TEM images. (c) The size distribution.
(d) The lattice fringes and (e) the SAED pattern taken from the dashed region in Fig. S4b,† respectively. The separated EDS mappings correspond
to (f1) Bi, (f2) Fe and (f3) O elements, respectively. The scale bar in (e) is 2 nm1.
particle doped SMOs29 or SMO heterojunctions.28,30 Interest-
ingly, bismuth ferrite, as a ferroelectric material, enables both
perovskite (BiFeO3) and sillenite (Bi25FeO40) to be presented,34
with which gas sensors are built, showing a specic sensing
response to acetone,35 SO2 (ref. 36) and NH3.37 Apparently, the
internet of things requires that fewer sensors are integrated for
minimized size, however, to endow more functions and
stronger performance.38,39 Being inspired by this, if n/p semi-
conducting transition of sensing materials, e.g., perovskite-
BiFeO3 and sillenite-Bi25FeO40 hetero-nanostructures, could be
modulated by such parameters as temperature and geometrical
size, individual gas sensor prototypes might be able to selec-
tively detect binary target gases (e.g., H2S and acetone
biomarkers).
In this study, selective detection of binary H2S and acetone
biomarkers has been developed via temperature-modulated n/p
transformation of interconnected BiFeO3/Bi25FeO40 nano-
particles (NPs). The BiFeO3/Bi25FeO40 NPs of
22.5 nm diam-
eter were obtained by microwave hydrothermal and subsequent
annealing methods, as is schematically shown in Fig. S1.†
Detection of H2S (n-type mode) and acetone (p-type mode)
biomarkers via a single BiFeO3/Bi25FeO40 NP sensor prototype
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has been studied. Remarkably, the sensors present superior
stability and a low detection limit of 100 ppb H2S (Ra/Rg  1 ¼
21.5%) and 500 ppb acetone (Rg/Ra  1 ¼ 10.0%). Also, the
simulated breath sensing of both H2S and acetone biomarkers
is of potential in early-diagnosis of halitosis and diabetes.
Moreover, the sensors with a waterproof membrane were tested
by critically immersing them in water for 120 min. Theoreti-
cally, the n/p semiconducting transition is ascribed to separated
electron–hole pairs of interconnected BiFeO3/Bi25FeO40 NPs,
regulated by ionization of adsorbed oxygen molecules. As
a result, such temperature-modulated n/p transition sensing of
BiFeO3/Bi25FeO40 NPs enables the selective detection of H2S (n-
type mode) and acetone (p-type mode) biomarkers, which
contribute to the integration and miniaturization of sensor
prototypes.
2. Results and discussion
2.1 Synthesis and characterization of BiFeO3/Bi25FeO40 NPs
The BiFeO3/Bi25FeO40 NPs in our case were synthesized by
combined microwave hydrothermal treatment of Bi(NO3)3 and
Fe(NO3)3 in alkaline media and subsequent annealing. The
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Fig. 2 XRD, Mott–Schottky plot and XPS characterization of BiFeO3/Bi25FeO40 NPs. (a) XRD patterns, (b) Mott–Schottky plot and (c) the XPS
survey spectrum of the interconnected BiFeO3/Bi25FeO40 NPs. High-resolution XPS spectra are related to (d) Bi 4f, (e) Fe 2p and (f) O 1s,
respectively.
synthetic details are demonstrated in the Experimental
section.† The chemical reactions are summarized as follows:40
Bi(NO)3 + Fe(NO)3 + 6KOH / Bi(OH)3 + Fe(OH)3 +
6KNO3 (1)
Bi(OH)3 + Fe(OH)3 / BiFeO3 + 3H2O
2BiFeO3 + 48Bi(OH)3 + O2 / 2Bi25FeO40 + 72H2O
In our experiments, the synthetic parameters of microwave
hydrothermal treatment, such as temperature, duration and
chemical composition of the precursors, are essential to form
the BiFeO3/Bi25FeO40 NPs. In particular, the annealing condi-
tions, such as temperature and heating rate, play a critical role.
We tried the experiments without annealing, and found the
presence of Fe2O3 phase (Fig. S2†), which is ascribed to the
thermal decomposition of Fe(OH)3. Meanwhile, in the process
of calcination at high temperature, Bi(OH)3 rstly decomposes
into Bi2O3 and then reacts with Fe2O3 to form BiFeO3, and the
mixed phases of BiFeO3 and Bi25FeO40 are nally obtained.
Otherwise, if other concentrations of polyethylene glycol (PEG)
and KNO3 were employed, NPs with large diameter and uneven
size distribution were obtained, as shown in Fig. S3a–c.†
For morphological observation of BiFeO3/Bi25FeO40 NPs,
SEM and TEM characterizations were conducted as shown in
Fig. 1a and b. One can see that the NPs are uniform and gran-
ular in appearance, and the average diameter of the NPs has
been analysed to be
22.5 nm (Fig. 1c). From closer observation
in Fig. S4a,† the BiFeO3/Bi25FeO40 NPs overlap and form inter-
connected NPs. To investigate the crystallization of the
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interconnected BiFeO3/Bi25FeO40 NPs, HRTEM and selected
area electron diffraction (SAED) analysis were performed on the
dashed region in Fig. S4b.† From Fig. 1d, in the HRTEM image,
the interplanar spacings of d ¼ 0.184 nm and 0.317 nm agree
with the (521) and (310) planes of Bi25FeO40, respectively.
Meanwhile, that of d ¼ 0.279 nm is assigned to the (110) plane
(2) of BiFeO3. Diffractive spots and rings coexist in the SAED
pattern in Fig. 1e and S4c† (the raw data), which reveals the
(3)
polycrystalline nature of the BiFeO3/Bi25FeO40 NPs, agreeing
with the lattice fringes (Fig. 1d) and XRD (Fig. 2a) analysis. The
diffractive spots are attributed to excellent crystallization in the
characterized region. In addition, to identify the chemical
components of the interconnected BiFeO3/Bi25FeO40 NPs, the
elemental mappings of Fig. 1f are exhibited in Fig. 1f1–f3,
revealing that Bi, Fe and O are distributed uniformly.
The XRD pattern in Fig. 2a reveals the phase of inter-
connected BiFeO3/Bi25FeO40 NPs. Accordingly, the diffractive
peaks agree well with the two-phase coexistence of BiFeO3
(rhombohedral crystal, JPCDS no. 86-1518) and Bi25FeO40 (cubic
crystal, JPCDS no. 46-0416). To investigate the Schottky contacts
of the interconnected BiFeO3/Bi25FeO40 NPs, we carried out
Mott–Schottky analysis by means of a mono-frequency capaci-
tance–voltage (C–V) sweep as shown in Fig. 2b, from which the
plots with a positive slope reveal the n-type semiconducting
feature.4,41 The surface chemical composition and valence state
of the interconnected BiFeO3/Bi25FeO40 NPs are essential for the
sensing performance, and XPS analysis was thus carried out.
Apparently, the survey spectrum in Fig. 2c presents Bi, Fe and O
elements, respectively. Moreover, the Bi 4f spectrum in Fig. 2d
shows both peaks located at 158.83 and 164.08 eV, which
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correspond to the Bi3+ and Bi5+, respectively.42 Similarly, it has
been conrmed that the formula of Bi25FeO40 is Bi243+(Bi5+Fe3+)
O40, in which Bi3+ ions occupy the octahedral positions, whereas
the Bi5+ and Fe3+ ions share the tetrahedral positions.42,43 In the
Fe 2p highly-resolved spectrum (Fig. 2e), the binding energies of
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710.59 eV (Fe 2p3/2) and 724.04 eV (Fe 2p1/2) with a satellite peak
at 719.84 eV agree well with Fe3+.42,44 Meanwhile, Fig. 2f shows
the highly-resolved spectrum of O 1s, from which two tted
peaks corresponding to lattice oxygen and chemisorbed oxygen
are observed at 529.93 and 531.14 eV, respectively. From the
integrated area, the chemisorbed oxygen is calculated to be
41.54%. Accordingly, it has been proven that multivalent tran-
sition metal oxides are able to adsorb more surface oxygen,32
suggesting high oxygen adsorption on the surface of the inter-
connected BiFeO3/Bi25FeO40 NPs.
2.2 Temperature-modulated n/p semiconducting transition
As the temperature-dependent n/p transition plays a pivotal role
in modulating the sensing behavior of interconnected BiFeO3/
Bi25FeO40 NPs, we elaborately evaluated the real-time resistance
under operating temperatures from 160  C to 400  C toward
100 ppm formaldehyde, ethanol, toluene and acetone, and
10 ppm H2S (Fig. 3a–e). One can see that the real-time resistance
curves of the BiFeO3/Bi25FeO40 NPs sensor display n-type sem-
iconducting features below
300  C toward the above-
mentioned target gases. The behavior of the n/p semi-
conducting transition occurs at 260–300  C, except for in an
ethanol atmosphere (300–340  C). In contrast, the sensing
response dominated by a p-type mode was observed from 300  C
to 400  C toward formaldehyde, toluene, acetone and H2S, and
340–400  C to ethanol. Accordingly, the critical temperature of
Fig. 3 Sensing-resistance curves of the BiFeO3/Bi25FeO40 NPs sensor prototype towards various target gases. 100 ppm (a) formaldehyde, (b)
ethanol, (c) toluene and (d) acetone, and (e) 10 ppm H2S at various working temperatures. (f) The summarized response histogram. The relative
humidity (RH) of the above test is
30%.
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the n/p sensing transition may vary with the applied target
gases, and it exists within a temperature range. Additionally, n-
and p-type mixed modes responses appear, which are marked
with red dashed circles in Fig. 3a–e. As a result, the above
responses are summarized in Fig. 3f, from which the sensing
responses show the best selectivity to H2S at 200  C and present
n-type mode dominations. Meanwhile, under the p-type sensing
mode, the best selectivity to acetone is seen at 300  C.
To investigate the concentration-dependent n/p transition
sensing, we have tested the sensing responses to 0.1–1 ppm H2S
and 0.5–2 ppm acetone at the working temperatures of 160–
400  C (Fig. S5 and S6†), and one can see that the n/p transition
does not occur in this concentration region. Notably, the
BiFeO3/Bi25FeO40 NP sensor prototypes show n-type sensing of
0.1–10 ppm H2S at 200  C (Fig. 4b and f) and p-type sensing of
0.5–10 ppm acetone (Fig. 5b) at 300  C, respectively, and do not
display a concentration-dependent n/p transition below
10 ppm. Therefore, the working temperature is the key factor for
the n/p semiconducting transition of the BiFeO3/Bi25FeO40 NPs
in our cases. In particular, compared to the other n/p sensing
transition,27–33 our sensors are able to selectively detect H2S (n-
mode) and acetone (p-mode) via modulating the n/p transition.
2.3 Selective detection of H2S and acetone biomarkers
To gain insight into the sensing performance, the performance
of the BiFeO3/Bi25FeO40 NPs sensor toward the H2S biomarker
under n-type sensing mode was evaluated rst. From Fig. 4a, we
observed that the sensor shows a maximum response (Ra/Rg  1
¼ 1.95) at the optimal operating temperature of
200  C.
Meanwhile, the real-time response plots of H2S (100 ppb to 1
ppm) in Fig. 4b show an excellent linear relationship between
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Fig. 4 Under n-type mode, the sensing performance of the BiFeO3/Bi25FeO40 NPs sensor prototypes toward H2S at 200  C and RH of
30%. (a)
The responses to 1 ppm at various temperatures. (b) The real-time response towards 0.1–1 ppm. (c) The repeatability, (d) selectivity, (e) interferent
selectivity and (f) long-term stability, respectively. Interfering gas mixtures in (e) include ethanol, acetone, toluene, formaldehyde, CO and H2, of
which the concentration applied is ten times as that of the target H2S.
Fig. 5 Under p-type mode, the sensing performance of the inter-
connected BiFeO3/Bi25FeO40 NPs sensor prototype toward acetone at
300  C and RH of
30%. (a) The responses to 1 ppm acetone at various
temperatures. (b) The real-time response curve towards 0.5–10 ppm
acetone. The sensing evaluations correspond to (c) selectivity and (d)
short-term and long-term stability, respectively.
the responses and gas concentrations. Also, the repeated
stability towards 5 ppm H2S is shown in Fig. 4c. The response
and recovery time of theBiFeO3/Bi25FeO40 NPs sensor toward
1 ppm H2S are 32 s and 68 s (Fig. S7†), respectively. In particular,
we purposely compared the response toward 10 ppm H2S, with
those toward 100 and 1000 ppm of other interfering gases, and
found that the responses in Fig. 4d towards the interfering
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gases were negligible. Additionally, we investigated the inter-
ferent selectivity in Fig. 4e, from which the responses of the H2S
mixture are observed to be close to those of the pure H2S,
further revealing the excellent selectivity of our BiFeO3/
Bi25FeO40 NPs sensors. Furthermore, we repeated the sensing
response in Fig. 4f on the 1st, 7th, 30th and 60th day under the
same evaluation conditions, and one can see that the sensing
responses are almost the same, exhibiting great stability.
Similarly, the sensing performance of the BiFeO3/Bi25FeO40
NPs toward the acetone biomarker under p-type sensing
behavior was investigated as well. The optimum working
temperature was found to be
300  C toward 1 ppm acetone in
Fig. 5a. Fig. 5b shows the real-time responses, and one can
observe that in p-type mode, acetone can be detected as low as
0.5 ppm. Furthermore, Fig. 5c shows the selectivity of the
BiFeO3/Bi25FeO40 NPs sensor to acetone at 300  C, and the
interfering gases are well excluded. Also, the interferent selec-
tivity is investigated in Fig. S8a and b,† which further veries
that the sensor is capable of selectively detecting acetone.
Additionally, the sensor presents excellent short-term and long-
term stability by circular testing toward 2 ppm acetone at
a certain time interval (Fig. 5d). Remarkably, our BiFeO3/
Bi25FeO40 NPs sensor exhibits high response to H2S and low
detection limit to both acetone and H2S biomarkers, compared
with the unsatisfactory sensing performance of BiFeO3-based
sensors (Table S1†). For practical application, we investigated
the feasibility of breath gas analysis with the BiFeO3/Bi25FeO40
NPs. In this way, the simulated halitosis and diabetes breath in
Fig. 6a was evaluated by mixing 1 ppm of H2S and acetone
inside the exhaled breath of healthy people.45 Accordingly, the
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response to the simulated patient breath was lower than that of
the pure biomarker in Fig. 6b and c. Nevertheless, it was much
higher than that of the healthy breath, so the patients can be
distinguished from healthy ones.
In particular, to avoid the interference of humidity, we
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simulated the relative humidity of exhaled breath, and the
response of the BiFeO3/Bi25FeO40 NPs under n-type and p-type
modes at a relative humidity of
55% and
85% was investi-
gated as shown in Fig. S9,† indicating that our sensors are able
to work even when the humidity reaches
85%. Notably, we
further tested the sensor prototypes to simulate the case of
working in critically wet conditions. Specically, we purposely
mounted an intake grid covered with waterproof membrane,
which is able to block water, only allowing the ventilation of the
target gases (e.g., H2S and acetone). In Fig. S10,† we sprayed
water over the “ventilating window” of the sensor prototype.
Even when the prototype was immersed in water for 120
minutes, it presented nearly the same sensing response aer
properly wiping off the surface water and drying the waterproof
membrane (Fig. 6d and e), and one can verify the experimental
details in the ESI Video.† As a result, our sensors have been
tested under critical conditions, and are able to resist the
inuence of humidity, thus showing potential in future gas-
sensing detection of biomarkers via practical breath diagnoses.
2.4 The sensing mechanism
The energy band of the BiFeO3/Bi25FeO40 NPs was used to
understand the n/p transition sensing mechanism. Accordingly,
the ultraviolet photoelectron spectroscopy (UPS) and ultraviolet-
visible (UV-vis) absorption spectra were obtained to determine
Fig. 6 The investigation of the breath gas analysis of the BiFeO3/Bi25FeO40 NPs sensor prototypes. (a) Practical simulation of the exhaled breath
of a healthy experimenter, the breath was collected using a tedlar bag and taken out with a syringe. The responses of (b) simulated halitosis
breath, 1 ppm H2S and healthy breath and (c) simulated diabetes breath, 1 ppm acetone and healthy breath. (d) The real-time response plot of the
sensor covered with a waterproof membrane being immersed in deionized water for 120 min was compared with the same sensor (e) without the
waterproof membrane.
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the band structure of the BiFeO3/Bi25FeO40 NPs. In Fig. S11a
and b,† the UPS valence band spectra show that the valence
band maximum (VBM) energy is around 2.67 eV.46 In Fig. S11c,†
the UV-vis absorption spectrum shows an absorption band in
the range of 200–400 nm, and the band gap value (Eg) is esti-
mated to be
3.16 eV by the plot of (ahn)1/2 versus (hn) in
Fig. S11d.†47 Correspondingly, the conduction band minimum
(CBM) is
0.49 eV according to eqn (4). Also, according to the
Mott–Schottky analysis in Fig. 2b, the interconnected BiFeO3/
Bi25FeO40 NPs are an n-type semiconductor, so the Fermi level
(EF) marked with a red dashed line is above the intrinsic Fermi
level (Ei) (Fig. 7a).
E(CBM) ¼ E(VBM)  Eg (4)
The surface-adsorbed oxygen molecules were ionized into
oxygen species (O2, O, O2) by the thermally stimulated
processes of oxygen adsorption, dissociation, and charge
transfer, which involve the electrons in the conducting band.
The reactions are presented in eqn (5)–(7).48–50
O2(ads) + e / O2(ads) (5)
O2(ads) + e / 2O(ads) (6)
O(ads) + e / O2(ads) (7)
In our cases, the critical temperature is 260–340  C, below
which the adsorption of oxygen species (O2, O) leads to the
reduction of electrons and the formation of an electron deple-
tion layer (Fig. 7b). When reducing gas H2S reacts with O (eqn
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Fig. 7 Schematic energy-band variation. (a) Flat band situation with n-type conductivity, (b) oxygen adsorption leads to a depletion layer and n-
type surface conductivity or (c) an inversion layer (the EF lies below the Ei) and p-type surface conductivity. The sensing mechanism diagrams of
the interconnected BiFeO3/Bi25FeO40 NPs sensor prototype. (b1) N-type sensing mode and (c1) p-type sensing mode, respectively.
(8)), electrons are released back to the conduction band, nar-
rowing the electron depletion layer, and thus presenting n-type
mode (Fig. 7b1). In contrast, in p-type mode, when the working
temperature rises, strong adsorption of the oxygen atom (O2)
captures more electrons, leading to the formation of an inver-
sion layer on the BiFeO3/Bi25FeO40 NPs surface,31,51 which is
marked with orange dashed boxes in Fig. 7c. In this case, the EF
lies below the Ei, and the main carriers are holes on the BiFeO3/
Bi25FeO40 NPs surface, resulting in p-type surface conductivity.
When acetone reacts with O2, holes are consumed (eqn (9)),
narrowing the hole accumulation layer (Fig. 7c1).
 
H2S(ads) + 3O (ads) / H2O + SO2 + 3e (8)
CH3COCH3(ads) + 8O 2
(ads) + 16h / 3CO2 + 3H2O
+
(9)
For the response of n- and p-type mixed modes marked with
red dashed circles in Fig. 3a–e, we interpret this as the transient
change of majority carriers on the surface of the BiFeO3/
Bi25FeO40 NPs. Specically, under p-type sensing, the majority
carriers of holes react with the high concentration reducing
gases and are signicantly consumed, and nally the electrons
become the majority carriers. In comparison, when the sensor
prototypes are exposed to air, strong adsorption of oxygen
atoms (O2) will form an inversion layer again. Additionally, it
should be noted that the BiFeO3/Bi25FeO40 NPs may contribute
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to the n/p transition sensing, and their separated band struc-
tures of BiFeO3 and Bi25FeO40 can be found in the Band struc-
ture section.† In short, the formation of the BiFeO3 and
Bi25FeO40 heterojunctions induces band-bending, which
promotes highly isolated thermal-stimulated carriers.28 In these
cases, the equilibrium of the separated electrons and holes is
modulated by the temperature-dependent ionization reaction of
the surface-adsorbing oxygen, and nally promotes the n/p
transition sensing.
3. Conclusions
In summary, a single sensor detecting dual H2S and acetone
biomarkers has been developed, via modulating the n/p semi-
conducting transition of interconnected BiFeO3/Bi25FeO40 NPs.
Meanwhile, the n/p semiconducting transition has been
experimentally observed. Remarkably, the BiFeO3/Bi25FeO40
NPs sensor prototypes exhibit ppb-level detection limit and
excellent stability in both n- and p-type modes. Signicantly,
human breath sensing has been simulated for both H2S and
acetone biomarkers, and provides an experimental basis for
practical application in early-diagnosis of halitosis and dia-
betes. Moreover, the sensors with a waterproof membrane were
evaluated by critically immersing them in water for 120 min.
The mechanism of this n/p type transition sensing is attributed
to the synergistic effect on temperature-dependent ionization of
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adsorbed oxygen molecules and semiconducting band-bending
of BiFeO3/Bi25FeO40 NPs. The dual n/p semiconducting types
are modulated by the working temperature parameters, which
enables the monitoring of two biomarkers, and thus this
method could be employed to design miniaturized gas sensors
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and multi-disease diagnosis by means of human breath. Future
theoretical investigations are expected on the n/p semi-
conducting transition of interconnected BiFeO3/Bi25FeO40 NPs.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
This work was nancially supported by the National Natural
Science Foundation of China (Grant No. 52072184), the
Fundamental Research Funds for the Central Universities,
Nankai University (Grant No. 63201179), and International
Research Fellow of the Japan Society of the Promotion of
Science (JSPS, Postdoctoral Fellowships for Research in Japan
(Standard), P18334).
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