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DOI: 10.1039/C9CC05881H

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Surface oxygen vacancy defect engineering of p-CuAlO2 via Ar&H2

plasma treatment for enhancing VOCs sensing performances
Received 00th January 20xx, Bin Tong, ab Gang Meng, *ac Zanhong Deng, ac Mati Horprathum, d Annop Klamchuen e and
Accepted 00th January 20xx Xiaodong Fang *ac

ChemComm Accepted Manuscript

DOI: 10.1039/x0xx00000x
Published on 04 September 2019. Downloaded on 9/5/2019 2:53:49 AM.

Ar&H2 plasma treatment was proposed to enhance the response of correlation between oxygen vacancy (VO) related (deep level)
p-CuAlO2 sensor toward volatile organic compounds. defects and (NO2) response.7 Li Y. X. et al. and Tong B. et al.
Comprehensive defect characterizations indicate a substantial reported the boosting of response via introducing singly ionized
increase of surface unsaturated oxygen vacancy (VO) defects via oxygen vacancy ( VO• ) defects.8, 9 Recent theoretic and
plasma treatment, which could provide active sites for molecule experimental works suggest VO defects on the surface could act
adsorption and the subsequent interfacial redox reaction. as the active sites for molecule adsorption and the subsequent
redox reactions.10-14 On the contrary, defects in the inner part
Owing to the compositional diversity, p-type delafossite ABO2 were generally detrimental for the device performance
(A: Cu, Ag, B: Al, Sc, Fe, Cr, Ga, etc.) oxide semiconductor based (typically act as carrier scattering or recombination center).
sensors potentially allow to extract sufficient features of Nevertheless, the widely used VO defect engineering
different adsorbed gas molecules from their electrical response approaches, either in-situ synthesis or (vacuum or reducing
signals, which is highly required for indoor/outdoor air quality atmosphere) post-annealing, typically create defects both on
and personal health monitoring, in the emerging trillion-sensor the surface and the inner part. Future advanced sensors
world.1-4 However, the intrinsic low response of p-type oxide (photo/electrochemical catalysts, and other semiconductor
semiconductor sensors, particularly toward volatile organic devices) rely on the capability of precisely (even at atomic scale)
compounds (VOCs), stemming from a ‘hole accumulation layer’ tailoring/ introducing the surface defects, without affecting the
configuration in ambient atmosphere,5 hinders their promising inner properties, while it remains a challenge.15
applications in the environment and personal health monitoring. In this work, low-power Ar&H2 plasma treatment was applied
Because oxide semiconductor sensor operates on the basis of to tailor the surface VO defects of p-type delafossite CuAlO2
an interfacial charge interaction between (adsorbed) molecule sensor. Besides the physical ion-bombardment of Ar plasma, H2
and oxide surface, the surface physiochemical properties of was dissociated into reactive H species which would chemically
oxide plays an important role for the electrical response, and react with the surface of CuAlO 2 powder via multiple
thus have been extensively investigated in the past few collisions.16 Gas response experiments demonstrate a
decades.6 Besides the extrinsic defects induced by doping, significant enhancement of response toward VOCs molecules
decoration, etc.,5 recent studies have indicated the intrinsic via Ar&H2 plasma treatment for 30 minutes. In line with VOCs
(surface) defects of oxide semiconductor could also play a vital response, comprehensive defect characterizations suggest a
role for molecule response (and photoelectrochemical catalyst formation of VO defect-rich layer via plasma treatment for 30
etc.). For examples, Ahn M. W. et al. reported the positive minutes, as evidenced by negligible variation of both
morphology and crystal phase, but a substantial increase of
surface VO components (X-ray photoelectron spectroscopy, XPS
a. Anhui Provincial Key Laboratory of Photonic Devices and Materials, Anhui
O 1s spectrum), singly ionized oxygen vacancies (electron spin
Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei,
230031, China. Email: menggang@aiofm.ac.cn, xdfang@aiofm.ac.cn resonance, ESR) and appearance of defect-related green
b. University of Science and Technology of China, Hefei 230026, China
emission (photoluminescence, PL).
c. Key Lab of Photovoltaic and Energy Conservation Materials, Chinese Academy of
Sciences, Hefei 230031, China
d. Opto-Electrochemical Sensing Research Team, National Electronic and Computer
Technology Center, PathumThani 12120, Thailand
e. National Nanotechnology Center, National Science and Technology Development

Agency, Pathum Thani 12120, Thailand

† Electronic Supplementary Information (ESI) available. See
DOI: 10.1039/x0xx00000x

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(0 1 11) (which is detrimental for the carrier transport). Under

View the
Article Online
(a) (b) (0 0 12)
(0 1 8)
(c) excitation of radiofrequency (i.e. 13.56 DOI:
MHz),10.1039/C9CC05881H
H2 molecules in
(0 0 9)
(0 1 2)
(1 0 4)
(1 0 7)
Ar&H2 mixture are prone to be dissociated into reactive H
(1 1 0)
5 1/nm (1 0 10)
(1 1 6)
plasma,23 which would easily react with the surface oxygen ions
with weak (unsaturated) chemical bonds via ion bombardment,
2 nm
and results in the formation of a VO defect-rich layer on the top
surface of sensing layer. We have examined the impact of Ar&H2
(d) plasma treatment on the VOCs molecule detection. Fig. 2(a)
shows the response (defined as ΔR/Ra, ΔR = Rg − Ra, where Rg
and Ra are sensor resistance in VOCs and synthetic air,
respectively) toward 100 ppm ethanol. Ar&H2 plasma treatment
could steadily improve the sensor response, particularly at the
elevated operation temperature. At 300 °C, the response of
pristine CuAlO2 sensor is 0.72, while the response of PT-30, PT-

ChemComm Accepted Manuscript

60 and PT-90 are 1.85, 1.50 and 1.08, respectively. Upon 30 min
Ar&H2 plasma treatment, surface oxygen of (pristine) CuAlO 2 is
prone to be firstly etched, resulting an increase of surface V O
Fig. 1 Morphological and structural characterizations of CuAlO2 defects, which may facilitate molecule/oxide interfacial charge
Published on 04 September 2019. Downloaded on 9/5/2019 2:53:49 AM.

particles. (a) SEM image. (b) TEM image and SAED pattern in the exchange and an enhancement of response. Meanwhile,
inset. (c) HRTEM image. (d) XRD pattern. The diffraction peaks plasma treatment would diminish the hole (Cu deficiency/
marked by * are the kβ lines of (006), (101), (012) and (018), vacancy and interstitial oxygen) 24, 25 concentration in p-CuAlO2
respectively. via altering the surface stoichiometry (extracting oxygen).
Whereas, further increasing treatment time may etch surface
CuAlO2 particles were obtained by sol-gel method,17 the Cu and/or Al ions, which would introduce more acceptor (i.e. Cu
detailed synthesis process and characterizations could be found vacancy).24, 25 In line with the above expectation, the base
in the supplementary material. SEM (Fig. 1(a)) and TEM (Fig. resistance of CuAlO2 sensor firstly increases, and then decreases
1(b)) indicate irregular particles with grain size ranging from ~10 with elongating Ar&H2 plasma treatment, as seen in Fig. S4.
nm to 5 μm. Both SAED (inset of Fig. 1(b)) and HRTEM (Fig. 1(c)) Therefore, we next focus on the comparison between pristine
suggest the polycrystalline nature of as-synthesized CuAlO2 and PT-30 sensor. The response enhancement of PT-30 sensor
particles, with a preferential stacking along (012) plane. XRD could be clearly observed from transient response curves
result (Fig. 1(d)) indicates a dominant 3R-CuAlO2 (space group toward 0.5 – 500 ppm ethanol shown in Fig. 2(b). Both sensors
of R3m) phase, trace 2H-CuAlO2 phase exists in the present possess good reproducibility properties, as depicted by the
CuAlO2 particles due to the small formation energy difference
between these two phases.18 Beside delafossite CuAlO2, no
other CuOx and AlOx related impurity phases were observed.
As-synthesized CuAlO2 particles were then coated onto a thin
alumina substrate with micro-interdigital electrodes, the local
temperature of sensing layer (thickness is about 15 μm, see
cross-sectional image in Fig. S1) was programmed by a Pt
microheater.9 After the aging of CuAlO2 sensors at 350 °C,
surface VO defects were tailored by Ar&H2 plasma treatment.
The CuAlO2 sensors herein are referred to as pristine, PT-30, PT-
60 and PT-90. VOCs response properties were examined in
SD101 sensing system (Hua Chuang Rui Ke Technology Co., Ltd.),
additional details on sensor fabrication and measuring
conditions are provided in supplementary material. Present
plasma treatment (30 – 60 min) doesn’t cause any detectable
impurity phases (examined by fine XRD scan shown in Fig. S2),
and noticeable variation of surface morphology/ roughness
(SEM images in Fig. S2).
Fig. 2 VOCs molecule response of pristine and Ar&H2 plasma
Similar with (photo)electrochemical catalyst,11, 15, 19, 20 the
treated CuAlO2 sensors. (a) Response toward 100 ppm ethanol
surface defects, including VO, typically act as active sites and
versus operation temperature. (b) Dynamic response curves
facilitate various surface redox reactions. Differing from
toward 0.5 – 500 ppm ethanol at 300 °C. (c) Reproducibility test
traditional thermal annealing process, low power plasma
for 100 ppm ethanol at 300 °C. (d) Response to different VOCs
treatment offers a simple but effective process to tailor the
with fixed concentration of 100 ppm at 300 °C.
superficial layer,21, 22 i.e. several nm beneath the surface,16
without introducing additional defects within the particle

2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

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Journal Name
multicycle measurements (toward 100 ppm ethanol) shown in
Fig. 2(c). Moreover, PT-30 CuAlO2 sensor shows increased
response toward various VOCs molecules, such as acetone and
n-hexane, shown in Fig. 2(d), demonstrating a (universal)
enhancement of VOCs/CuAlO2 interfacial charge exchange.
Increase of sensor resistance upon exposure to (reducing) VOCs
infers a p-type conductivity of both pristine and PT-30 CuAlO2
sensors, which is consistent with Mott-Schottky measurements
shown in Fig. S5.
XPS Cu 2p XPS O 1s
(a) (b)
Pristine
Published on 04 September 2019. Downloaded on 9/5/2019 2:53:49 AM.
PT-30
(c) ESR (d) PL
Pristine
PT-30
Pristine
Fig. 3 Defect characterizations of pristine and PT-30 CuAlO2. (a)
XPS Cu 2p spectra. (b) XPS O 1s spectra. (c) ESR spectra. (d)
Photoluminescence spectra.
In order to identify the underlying mechanism responsible for
the response enhancement, comprehensive defect
characterizations have been carried out. As one of surface-
sensitive (typically several nm) quantitative spectrometric
method, X-ray photoelectron spectroscopy (XPS) was utilized to
probe the chemical shifts of surface elements. Pristine CuAlO 2
possesses Cu+ with Cu 2p1/2 peak (centered at 952.6 eV), Cu
2p3/2 peak (at 932.8 eV) and energy gap of 19.8 eV. 26 Negligible
chemical shift of Cu 2p was detected via 30 min Ar&H2 plasma
treatment (PT-30), as seen in Fig. 3(a). On the contrary, we could
observe a clear difference of asymmetric O 1s spectrum, which
arises from three different components (OⅠ: lattice oxygen
centered at 530.5 eV, OⅡ: unsaturated oxygen vacancy
(including surface dangling oxygen bonds, in-plane VO, bridging
VO, etc.) 27 centered at 531.7 eV and OⅢ: chemisorbed oxygen
located at 532.8 eV),9, 20 as presented in Fig. 3(b). Pristine
CuAlO2 exhibits less oxygen vacancy (23.4%) and chemisorbed
oxygen (5.1%) components, and mainly comprises of lattice
oxygen (71.5%). While, Ar&H2 plasma treated PT-30 possesses
much more surface unsaturated oxygen vacancy (39.7%) and
chemisorbed oxygen (51.6%), lattice oxygen component only
make up 8.7%. In addition, PT-60 also exhibits a high oxygen
vacancy (35.7%) component, as seen in Fig. S6. A positive
This journal is © The Royal Society of Chemistry 20xx
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correlation between oxygen vacancy and VOCs response was
View Article Online
observed. Further boosting the sensingDOI: 10.1039/C9CC05881H
performances can be
anticipated by extending the VO engineering across the whole
sensing layer, i.e., via either multiple (thin layer) coating-
treating, or directly coating the plasma treated powder.28 It
should be noted that the plasma induced VO defects may be
slowly compensated under air (oxygen-rich) atmosphere at
elevated operation temperature, as indicated by stability
measurement shown in Fig. S7. Improving the stability of VO
defects29 will be another important topic beyond the scope of
present work. In comparison with previously reported V O
engineering approaches, including vacuum annealing,
controlling crystallization process, etc., present Ar&H 2 plasma
treatment offers us a facile and effective approach on
ChemComm Accepted Manuscript
Pristine
engineering surface VO defects, which are essential for
activating various surface redox reactions.9, 12, 14 VO defects
were further resolved by electron spin resonance (ESR), a
sensitive tool to probe the unpaired electrons trapped in V O
PT-30
defects (so-called singly ionized VO defect)8. In line with XPS O
1s spectrum, a drastic increase of ESR intensity at g = 2.05 was
observed for Ar&H2 plasma treated PT-30 CuAlO2 from Fig. 3(c),
illustrating an increase of (singly ionized) V O defects (additional
ESR results can be found in Fig. S8). Recent theoretic and
experimental works have demonstrated that singly ionized V O
defects could facilitate not only the adsorption of analyte, but
also the subsequent surface redox reactions,7-9, 12 resulting in a
PT-30
drastic performance enhancement of gas sensors,
(photo)catalysts, etc. Compared with conventional vacuum
annealing and in-situ synthesis, present Ar&H2 plasma
treatment only creates the surface defects, without introducing
additional defects beneath the surface, which are detrimental
for performance. Photoluminescence (PL) spectrum offers an
alternative tool in identifying the presence of defect.
Delafossite (bulk) CuAlO2 possesses indirect and direct band
gaps of 2.97 and 3.47 eV,30, 31 respectively. The spectrum of
pristine CuAlO2 is dominated by near band emission (NBE)
centered around 405 nm. In contrast, PT-30 CuAlO2 exhibits a
weak NBE emission and a dominant green defect emission
centered at 558 nm, suggesting presence of (deep) defect states,
as shown in Fig. 3(d). Though such defect emission has not been
reported by previous reports, the appearance of such emission
(1.25 eV above the valance band (EV) of CuAlO2) should closely
relate with VO defect. Moreover, according to the theoretic
work reported by Hamada I. et al. the formation energy of V O
defect in CuAlO2 is higher than 6 eV,24 Ar&H2 plasma with ‘hot’
active reducing H species would effectively create VO defect
(just on the surface of CuAlO2).
In summary, we reported the sensitivity enhancement of p-
type CuAlO2 sensor toward VOCs molecules by Ar&H2 plasma
treatment. Comprehensive defect characterizations including
XPS and ESR spectrum indicate the VO defect-rich layer was
formed on the top surface of the sensor, which could act as
active sites for the VOCs molecule adsorption and facilitate the
subsequent interfacial charge exchange. In comparison with
(vacuum) annealing and other defect engineering methods,
plasma treatment offers a unique approach in creating only a
thin defect-rich layer without introducing additional defect
J. Name., 2013, 00, 1-3 | 3
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within the particle. Such defect-rich shell/defect-less core 18 B. J. Ingram, G. B. Gonzalez, T. O. Mason, D. Y.View Shahriari, A.
Article Online
heterostructure could effectively combine the merits of Barnabe, D. G. Ko and K. R. Poeppelmeier, DOI:Chem. Mater., 2004,
10.1039/C9CC05881H
activating the surface reaction and facilitating the carrier 16, 5616-5622.
transport, which provides valuable benefits in designing highly 19 S. M. Sun, M. Watanabe, J. Wu, Q. An and T. Ishihara, J. Am. Chem.
sensitive molecule sensors or efficient oxide catalysts at atomic Soc.,, 2018, 140, 6474-6482.
scale level. 20 J. Bao, X. Zhang, B. Fan, J. Zhang, M. Zhou, W. Yang, X. Hu, H.
We acknowledge the financial supports from CAS Pioneer Wang, B. Pan and Y. Xie, Angew. Chem., Int. Ed., 2015, 54, 7399-
7404.
Hundred Talents Program from Chinese Academy of Sciences,
21 H. Huang, Y. C. Lee, C. L. Chow, O. K. Tan, M. S. Tse, J. Guo and T.
National Natural Science Foundation of China (Grant No. White, Sens. Actuators, B, 2009, 138, 201-206.
11604339 and 11674324) and CAS-JSPS Joint Research Projects 22 E. P. Stuckert, C. J. Miller and E. R. Fisher, ACS Appl. Mater.
(GJHZ1891). We also thank the Key Lab of Photovoltaic and Interfaces, 2017, 9, 15733-15743.
Energy Conservation Materials, CAS, and Anhui Provincial Key 23 S. Nunomura, I. Sakata and K. Matsubara, Phys. Rev. Appl., 2018,
Laboratory of Photonics Devices and Materials. 10, 054006.
24 I. Hamada and H. Katayama-Yoshida, Phys. B, 2006, 376, 808-811.

ChemComm Accepted Manuscript

25 J. Tate, H. L. Ju, J. C. Moon, A. Zakutayev, A. P. Richard, J. Russell
and D. H. McIntyre, Phys. Rev. B, 2009, 80, 165206.
Conflicts of interest 26 L. Deng, F. Lin, Q. Yu, X. He, A. Liu, W. Shi and J. Feng, J. Mater.
There are no conflicts to declare. Sci., 2016, 51, 7491-7501.
Published on 04 September 2019. Downloaded on 9/5/2019 2:53:49 AM.

27 M. Al-Hashem, S. Akbar and P. Morris, Sens. Actuators, B, 2019,

DOI: https://doi.org/10.1016/j.snb.2019.126845.
References 28 L. Xu, Q. Q. Jiang, Z. H. Xiao, X. Y. Li, J. Huo, S. Y. Wang and L. M.
Dai, Angew. Chem., Int. Ed., 2016, 55, 5277-5281.
1 R. A. Potyrailo, Chem. Rev., 2016, 116, 11877-11923. 29 Q. P. Wu, Q. Zheng and R. van de Krol, J. Phys. Chem. C, 2012, 116,
2 H. Liu, Y. He, K. Nagashima, G. Meng, T. Dai, B. Tong, Z. Deng, S. 7219-7226.
Wang, N. Zhu, T. Yanagida and X. Fang, Sens. Actuators, B, 2019, 30 S. H. Chiu and J. C. A. Huang, Surf. Coat. Technol., 2013, 231, 239-
293, 342-349. 242.
3 K. H. Lee, B. Y. Kim, J. W. Yoon and J. H. Lee, Chem. Commun., 2019, 31 A. N. Banerjee and K. K. Chattopadhyay, J. Appl. Phys., 2005, 97,
55, 751-754. 084308.
4 Z. Deng, B. Tong, G. Meng, H. Liu, T. Dai, L. Qi, S. Wang, J. Shao, R.
Tao and X. Fang, Inorg. Chem., 2019, DOI:
10.1021/acs.inorgchem.9b01120.
5 H.-J. Kim and J.-H. Lee, Sens. Actuators, B, 2014, 192, 607-627.
6 S. Fukami, M. Taguchi, Y. Adachi, I. Sakaguchi, K. Watanabe, T.
Kinoshita, T. Muro, T. Matsushita, F. Matsui, H. Daimon and T. T.
Suzuki, Phys. Rev. Appl., 2017, 7.
7 M. W. Ahn, K. S. Park, J. H. Heo, J. G. Park, D. W. Kim, K. J. Choi, J.
H. Lee and S. H. Hong, Appl. Phys. Lett., 2008, 93.
8 Y. X. Li, B. Y. Zu, Y. N. Guo, K. Li, H. B. Zeng and X. C. Dou, Small,
2016, 12, 1420-1424.
9 B. Tong, Z. Deng, B. Xu, G. Meng, J. Shao, H. Liu, T. Dai, X. Shan, W.
Dong, S. Wang, S. Zhou, R. Tao and X. Fang, ACS Appl. Mater.
Interfaces, 2018, 10, 34727-34734.
10 V. Agarwal and H. Metiu, J. Phys. Chem. C, 2016, 120, 2320-2323.
11 Z. Wang, X. Mao, P. Chen, M. Xiao, S. A. Monny, S. Wang, M.
Konarova, A. Du and L. Wang, Angew. Chem., Int. Ed., 2019, 58,
1030-1034.
12 N. Zhang, X. Li, H. Ye, S. Chen, H. Ju, D. Liu, Y. Lin, W. Ye, C. Wang,
Q. Xu, J. Zhu, L. Song, J. Jiang and Y. Xiong, J. Am. Chem. Soc., 2016,
138, 8928-8935.
13 Y. Zhang, C. C. Wang, J. L. Fu, H. Zhao, F. Tian and R. J. Zhang,
Chem. Commun., 2018, 54, 9639-9642.
14 L. Zhang, X.-Y. Xie, H. Wang, L. Ji, Y. Zhang, H. Chen, T. Li, Y. Luo,
G. Cui and X. Sun, Chem. Commun., 2019, 55, 4627-4630.
15 C. C. Li, T. Wang, Z. J. Zhao, W. M. Yang, J. F. Li, A. Li, Z. L. Yang, G.
A. Ozin and J. L. Gong, Angew. Chem., Int. Ed., 2018, 57, 5278-
5282.
16 L. X. Qian, H. Y. Liu, H. F. Zhang, Z. H. Wu and W. L. Zhang, Appl.
Phys. Lett., 2019, 114, 113506.
17 Z. H. Deng, X. B. Zhu, R. H. Tao, W. W. Don and X. D. Fang, Mater.
Lett., 2007, 61, 686-689.

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