nanomaterials

Article
Three-Dimensional Porous Nitrogen-Doped NiO
Nanostructures as Highly Sensitive NO2 Sensors
Van Hoang Luan 1 , Huynh Ngoc Tien 2 ID
, Seung Hyun Hur 3 , Jong Hun Han 4 and Wonoh Lee 1, *
ID

1 School of Mechanical Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwangju 61186,
Korea; vhluan1986@gmail.com
2 Department of Chemical Engineering, University of South Carolina, 301 Main Street, Columbia, SC 29208,
USA; huynhngoctien@gmail.com
3 School of Chemical Engineering and Bioengineering, University of Ulsan, 93 Daehak-ro, Nam-gu,
Ulsan 44610, Korea; shhur@mail.ulsan.ac.kr
4 School of Chemical Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwangju 61186,
Korea; jhhan@jnu.ac.kr
* Correspondence: wonohlee@jnu.ac.kr; Tel.: +82-62-530-1682

Received: 11 September 2017; Accepted: 8 October 2017; Published: 11 October 2017

Abstract: Nickel oxide has been widely used in chemical sensing applications, because it has
an excellent p-type semiconducting property with high chemical stability. Here, we present a
novel technique of fabricating three-dimensional porous nitrogen-doped nickel oxide nanosheets
as a highly sensitive NO2 sensor. The elaborate nanostructure was prepared by a simple and
effective hydrothermal synthesis method. Subsequently, nitrogen doping was achieved by thermal
treatment with ammonia gas. When the p-type dopant, i.e., nitrogen atoms, was introduced in the
three-dimensional nanostructures, the nickel-oxide-nanosheet-based sensor showed considerable
NO2 sensing ability with two-fold higher responsivity and sensitivity compared to non-doped
nickel-oxide-based sensors.

Keywords: sensor; porous nanostructure; nickel oxide; nitrogen doping; NO2 gas sensor

1. Introduction
Nitrogen dioxide (NO2 ) is an important air pollutant because it contributes to the formation of
photochemical smog, which has significantly harmful impacts on human health. Public awareness
about the dangers of NO2 has increased the demand for detecting this hazardous gas with high
precision sensors composed of highly sensitive materials. Therefore, numerous approaches have
been suggested to detect NO2 at the ppm level [1–3]. Among the various types of gas sensors,
semiconducting metal oxide gas sensors have attracted much attention because of their low cost,
ease of production, simplicity of use, and ability to detect numerous gases, e.g., those using tungsten
trioxide, titanium dioxide, vanadium oxide, tin dioxide, and nickel oxide (NiO) [4–6].
NiO, a well-known stable p-type semiconducting metal oxide, has a high melting point (1960 ◦ C)
and excellent chemical stability. Therefore, it has been extensively employed as electrodes in lithium
ion batteries and supercapacitors, as electro-catalysts in combustion gas sensing, and in electrochromic
devices [7–9]. Furthermore, a novel nanostructure with a high specific surface area is essential for
enhanced performance of the NiO-based devices, which can be achieved by reactive sputtering, sol–gel
methods, and hydrothermal treatments [10–14]. Therefore, highly porous NiO nanostructures can
be used to fabricate highly sensitive gas sensors, especially for NO2 detection, because the p-type
semiconducting NiO can effectively donate electrons to the NO2 molecules.

Nanomaterials 2017, 7, 313; doi:10.3390/nano7100313 www.mdpi.com/journal/nanomaterials

Nanomaterials 2017, 7, 313 2 of 9

Nanomaterials 2017, 7, 313 2 of 9

Previous studies have reported that nitrogen (N) is a good dopant in many metal oxides because
N and oxygen have
electro-catalytic similar ionicinradii
performance the [15–17].
carbon N-doping
monoxidein gas
titanium dioxide
reaction effectively
[18], improved
and promoted NO its2
electro-catalytic performance
adsorption as proven in the carbon
theoretically monoxide
via density gas reaction
functional theory[18], and promoted
calculation NO2 adsorption
[19]. Furthermore, the
as proven theoretically via density functional theory calculation [19]. Furthermore,
intrinsic electrical resistance and signal noise level of metal oxides could be overcome via theN-doping
intrinsic
electrical
[20–22]. resistance and signal noise level of metal oxides could be overcome via N-doping [20–22].
Herein,
Herein, wewepresent
presentthree-dimensional
three-dimensional porous N-doped
porous NiO nanosheets
N-doped (NSs) for
NiO nanosheets highly
(NSs) forsensitive
highly
NO sensing
sensitive
2 applications. The elaborate NiO nanostructure was prepared by
NO2 sensing applications. The elaborate NiO nanostructure was prepared by a simple a simple and effective
and
solution-based hydrothermal
effective solution-based method [23,24].
hydrothermal method Subsequently, N-doping
[23,24]. Subsequently, was achieved
N-doping by thermal
was achieved by
treatment with ammonia gas. Figure 1 shows the N-doped NiO nanostructure
thermal treatment with ammonia gas. Figure 1 shows the N-doped NiO nanostructure used in NO2 used in NO 2 sensing.
The N-doped
sensing. The NiO nanostructure
N-doped is hydrothermally
NiO nanostructure grown on a silicon/silicon
is hydrothermally grown on a dioxide (Si/SiO2dioxide
silicon/silicon ) wafer
and gold
(Si/SiO (Au) electrodes are deposited to measure the electrical signals during NO2 exposure.
2) wafer and gold (Au) electrodes are deposited to measure the electrical signals during Owing
NO2
to
exposure. Owing to the N-doping effect with hierarchical nanostructure, the resistance changecan
the N-doping effect with hierarchical nanostructure, the resistance change in the gas sensor be
in the
greatly amplified. The result shows that the N-doped NiO-based gas sensor, compared
gas sensor can be greatly amplified. The result shows that the N-doped NiO-based gas sensor, to a non-doped
sensor,
compared exhibits a two-fold sensor,
to a non-doped higher responsivity and sensitivity
exhibits a two-fold toward NO2and
higher responsivity gassensitivity
detection and is thus
toward NOa2
candidate for highly sensitive
gas detection and is thus a candidateNO 2 sensors.
for highly sensitive NO2 sensors.

Figure 1. A schematic illustration and a top-view image of a three-dimensional

three-dimensional porous
porous N-doped
N-doped NO
NO22
gas sensor based on NiO nanosheets (NSs).
(NSs).

2. Materials and Methods

2.1. Synthesis of
2.1. Synthesis of the
the NiO
NiO Nanostructure
Nanostructure
The three-dimensional porous
The three-dimensional porousNiO NiOnanostructure
nanostructure waswas synthesized
synthesized via via sequential
sequential seeding
seeding and
and
growthgrowth [23,24],
[23,24], andand all all reagents
reagents werepurchased
were purchasedfrom from Sigma-Aldrich,
Sigma-Aldrich, Korea. Korea. Nickel
Nickel acetate
acetate
tetrahydrate
tetrahydrate (0.2 (0.2M)M)was
wasdissolved
dissolved inin a mixture
a mixture of 2-methoxyethanol
of 2-methoxyethanol (6 mL)
(6 mL) and diethanolamine
and diethanolamine (0.25
(0.25
mL) tomL) to obtain
obtain an NiOan NiO
seedseed solution.
solution. AfterAfter
thethe
seedseed solution
solution waswas stirred
stirred for2 2hhatatroom
for roomtemperature,
temperature,
it was spin-coated
spin-coated at at4000
4000rpmrpmforfor3030s sononanan Si/SiO ◦ C for
it was Si/SiO 2 wafer
2 wafer andand
drieddried
on aon a hot-plate
hot-plate at °C
at 250 250for 15 s.
15 s. After the spin-coating process was repeated threethe
times, the was
sample was annealed ◦C
After the spin-coating process was repeated three times, sample annealed at 400 °Catfor400
2 h in
for 2 h in achamber.
a vacuum vacuum Note chamber.
that aNote
higherthat a higher
rotating rotating
speed and aspeed
longer and a longer
spinning timespinning time may
may produce an
produce an irregular and/or thin coating layer owing to excessive centrifugal
irregular and/or thin coating layer owing to excessive centrifugal force. Here, we found that the above force. Here, we found
that the above
condition condition
was optimal forwas optimal for
constructing constructing
uniform uniform
and stable seed and
layerstable seed layer
with strong with strong
adhesion on the
adhesion
substrate on theAtsubstrate
[23]. the next[23]. Atan
stage, theNiO
nextgrowth
stage, an NiO growth
solution solution by
was prepared wasdissolving
prepared by dissolving
nickel nitrate
nickel nitrate (5.8
hexahydrate hexahydrate (5.8 g) and hexamethylenetetramine
g) and hexamethylenetetramine (4.8 g) (DI)
(4.8 g) in distilled in distilled (DI) water
water (100 (100NiO-
mL). The mL).
The NiO-seed-coated wafer was indipped in the growth ◦
seed-coated wafer was dipped the growth solutionsolution
at 90 °Catfor
90 2Ch,forrinsed
2 h, rinsed
with DIwith DI water,
water, and
and annealed at°C ◦ C for 1 h. The annealing process was performed in a gas chamber filled with
350for
annealed at 350 1 h. The annealing process was performed in a gas chamber filled with argon
argon
(1 atm)(1and
atm)ammonia
and ammonia (50 sccm)
(50 sccm) for N-doping.
for N-doping. Au electrodes
Au electrodes werewere
thenthen deposited
deposited on on
thethe surface
surface of
of
thethe N-doped
N-doped NiONiO nanostructure
nanostructure viavia thermal
thermal evaporation
evaporation in in vacuum.
vacuum.

2.2. Chracterization of the N-Doped NiO Nanostructure

The porous morphology of the synthesized NiO nanostructure was investigated by scanning
electron microscopy (SEM, JEOL JSM-6500FE, Tokyo, Japan). X-ray diffraction (XRD) measurements
Nanomaterials 2017, 7, 313 3 of 9

2.2. Chracterization of the N-Doped NiO Nanostructure

The porous morphology of the synthesized NiO nanostructure was investigated by scanning
electron microscopy (SEM, JEOL JSM-6500FE, Tokyo, Japan). X-ray diffraction (XRD) measurements
Nanomaterials 2017, 7, 313 3 of 9
Nanomaterials
were carried out 2017,to
7, 313
identify the crystal structure of NiO using a high-resolution X-ray diffractometer 3 of 9

(Rigaku, D/MAXZ-2500V,
were carried out to identify Tokyo,
the crystal Japan).
structure The Brunauer–Emmett–Teller
of NiO using a high-resolution(BET) specific surface
X-ray diffractometer
were carried out to identify the crystal structure of NiO using a high-resolution X-ray diffractometer
areas of the powders were determined by nitrogen adsorption
(Rigaku, D/MAXZ-2500V, Tokyo, Japan). The Brunauer–Emmett–Teller (BET) specific surface in a Micromeritics ASAP areas2020
(Rigaku, D/MAXZ-2500V, Tokyo, Japan). The Brunauer–Emmett–Teller (BET) specific surface areas
(Norcross, GA, USA)
of the powders werenitrogen
determinedadsorption apparatus.
by nitrogen adsorptionSuccessful N-doping ASAP
in a Micromeritics was examined by X-ray
2020 (Norcross,
of the powders were determined by nitrogen adsorption in a Micromeritics ASAP 2020 (Norcross,
GA, USA) nitrogen
photoelectron spectroscopy adsorption
(XPS) usingapparatus.
a Thermo Successful
FisherN-doping
Scientific wasESCALABexamined 250Xiby(Waltham,
X-ray
GA, USA) nitrogen adsorption apparatus. Successful N-doping was examined by X-ray
MA,photoelectron
USA). The spectroscopy
gas sensing (XPS) using awere
properties Thermo Fisher Scientific
evaluated by ESCALAB
measuring the 250Xi (Waltham,
resistance change MA, with
photoelectron spectroscopy (XPS) using a Thermo Fisher Scientific ESCALAB 250Xi (Waltham, MA,
USA). The
a Hewlett-Packardgas sensing
4155A properties were
semiconductor evaluated
parametric by measuring
analyzer in the resistance change with a Hewlett-
USA). The gas sensing properties were evaluated by measuring thearesistance
MST-5000changegas chamber (MS-Tech,
with a Hewlett-
Packard 4155A
Hwasung, semiconductor parametric analyzer inthe
a MST-5000 gas chamberan(MS-Tech, Hwasung,
Packard 4155A semiconductor parametric analyzer in a MST-5000 gas chamber (MS-Tech, Hwasung, of
Gyeonggi-do, Korea). In order to measure electrical resistance, Au layer consisting
Gyeonggi-do,
electrodes Korea). In
was deposited on order to measure
the surface the electrical
of the N-doped resistance, an using
NiO nanostructure Au layer consisting
a thermal of
evaporator
Gyeonggi-do, Korea). In order to measure the electrical resistance, an Au layer consisting of
electrodes
with a was
patterned deposited
mask. The on the
thickness surface
of theof the
Au N-doped
coat was NiO
50 nm nanostructure
from the top using
surface a thermal
of the NiO
electrodes was deposited on the surface of the N-doped NiO nanostructure using a thermal
evaporator with
nanostructure andaahadpatterned
a 10 µm mask. The thickness
spacing. of the Au coat
The concentration of NO waswas50 nm from the
carefully top surface
controlled of a
using
evaporator with patterned mask. The thickness of the Au coat was2 50 nm from the top surface of
the NiO nanostructure and had a 10 μm spacing. The concentration of NO2 was carefully controlled
massthe flow
NiO controller
nanostructure (GMC and1200,
had aATOVAC, Yongin,
10 μm spacing. The Gyeonggi-do,
concentrationKorea).
of NO2 was carefully controlled
using a mass flow controller (GMC 1200, ATOVAC, Yongin, Gyeonggi-do, Korea).
using a mass flow controller (GMC 1200, ATOVAC, Yongin, Gyeonggi-do, Korea).
3. Results and Discussion
3. Results and Discussion
3. Results and Discussion
3.1. Morphology of the N-Doped NiO-NS Nanostructure
3.1. Morphology of the N-Doped NiO-NS Nanostructure
3.1.The
Morphology of the N-Doped
three-dimensional NiO-NS
porous Nanostructureof N-doped NiO NSs (Figure 2) shows that the
nanostructure
The three-dimensional porous nanostructure of N-doped NiO NSs (Figure 2) shows that the
thickness Theand height of the grown
three-dimensional porous NSs were 20–30 of
nanostructure nmN-doped
and 1–3 NiOµm, respectively,
NSs (Figure 2) inshows
close agreement
that the
thickness and height of the grown NSs were 20–30 nm and 1–3 μm, respectively, in close agreement
with the previously
thickness and height reported valuesNSs
of the grown [23,24].
were The20–30 porous
nm and nanostructure hierarchically
1–3 μm, respectively, in closegrown on the
agreement
with the previously reported values [23,24]. The porous nanostructure hierarchically grown on the
withhad
wafer the apreviously
high surface reported
area ofvalues m22/g, suggesting
~205 [23,24]. The porousan nanostructure
enhanced gas hierarchically
adsorption grownability,on
and thecan
wafer had a high surface area of ~205 m 2/g, suggesting an enhanced gas adsorption ability, and can
wafer had a high surface area of ~205 m /g, suggesting an enhanced
thus be applied in high-performance NO2 sensors. Energy-dispersive X-ray spectrometry (EDS) gas adsorption ability, and can
thus be applied in high-performance NO2 sensors. Energy-dispersive X-ray spectrometry (EDS)
thus beanalysis
mapping appliedofinthe high-performance
elements is shown NO sensors.3. Energy-dispersive
in2 Figure Uniformly dispersed X-ray spectrometry
green and red dots (EDS)
on the
mapping analysis of the elements is shown in Figure 3. Uniformly dispersed green and red dots on
mapping
N-doped analysis of the elements is shown in Figure 3. Uniformly dispersed green and red dotsin on
the N-doped NiO NSs indicate the successful growth of NiO nanosheets. Note that the N-mappingthe
NiO NSs indicate the successful growth of NiO nanosheets. Note that the N-mapping
EDS the N-doped NiO NSs indicate the successful growth of NiO nanosheets. Note that the N-mapping
in spectrum was somewhat
the EDS spectrum unclear owing
was somewhat unclearto the strong
owing to intensity
the strong of Ni and O.ofThe
intensity Niidentification
and O. The of
inNthe EDS was
theidentification
element spectrum was via
examined somewhat
XPS unclear owing to the strong intensity of Ni and O. The
analysis.
of the N element was examined via XPS analysis.
identification of the N element was examined via XPS analysis.

2. 2.SEM
Figure
Figure SEMimages
imagesof
of(a)
(a)the
the three-dimensional nanostructureofofN-doped
three-dimensional nanostructure N-doped NiO
NiO NSs
NSs and
and (b)(b)
its its
Figure 2. SEM images of (a) the three-dimensional nanostructure of N-doped NiO NSs and (b) its
magnified
magnified image.
image.
magnified image.

Figure 3. EDS mapping images of N-doped NiO NSs (scale bar = 4 μm).
Figure3.3.EDS
Figure EDSmapping
mappingimages
images of
of N-doped
N-doped NiO
NiONSs
NSs(scale
(scalebar
bar= =4 4μm).
µm).
3.2. Crystallinity of the N-Doped NiO NS
3.2. Crystallinity of the N-Doped NiO NS
Figure 4 shows three distinguishable diffraction peaks at 37.2°, 43.5°, and 62.3°, corresponding
Figure 4 shows three distinguishable diffraction peaks at 37.2°, 43.5°, and 62.3°, corresponding
to the (111), (200), and (220) NiO planes, respectively, indicating high crystallinity for both N-doped
to the (111), (200), and (220) NiO planes, respectively, indicating high crystallinity for both N-doped
Nanomaterials 2017, 7, 313 4 of 9

3.2. Crystallinity of the N-Doped NiO NS

Figure 4 shows three distinguishable diffraction peaks at 37.2◦ , 43.5◦ , and 62.3◦ , corresponding
Nanomaterials 2017, 7, 313 4 of 9
to the (111), (200), and (220) NiO planes, respectively, indicating high crystallinity for both
N-doped and non-doped NiO NSs [7,20,24]. All reflections in the XRD pattern can be indexed
and non-doped NiO NSs [7,20,24]. All reflections in the XRD pattern can be indexed to face-centered-
to face-centered-cubic-phase NiO (JCPDS card #47-1049) [25]. Since both peak positions and intensities
cubic-phase NiO (JCPDS card #47-1049) [25]. Since both peak positions and intensities are almost the
are almost the same for N-doped and non-doped NiO NSs, it can be concluded that doping by nitrogen
same for N-doped and non-doped NiO NSs, it can be concluded that doping by nitrogen atoms has
atoms has no influence on the intrinsic crystal structure of NiO. The high peak intensity indicates
no influence on the intrinsic crystal structure of NiO. The high peak intensity indicates that the
that the prepared NiO NSs are highly crystalline. Moreover, for the N-doped NiO NSs, crystallinity
prepared NiO NSs are highly crystalline. Moreover, for the N-doped NiO NSs, crystallinity higher
higher than that of the non-doped NiO NSs can also be verified by calculating the grain sizes from
than that of the non-doped NiO NSs can also be verified by calculating the grain sizes from
crystallographic parameters. The Scherrer’s formula was used to calculate the crystallite size D of the
crystallographic parameters. The Scherrer’s formula was used to calculate the crystallite size D of the
manufactured NiO NSs using Equation (1) [26,27]:
manufactured NiO NSs using Equation (1) [26,27]:
0.9λ
0.9 λ
D=
D = β cos θ (1)
(1)
β cos θ
where λλ isisthe
thewavelength
wavelengthofofthe the X-ray
X-ray source
source (1.54
(1.54 Å), Å), is full
β is βthe the width
full width atmaximum
at half half maximum of
of high-
high-intensity
intensity peaks,peaks,
and θ and is the Bragg’s
is theθ Bragg’s angle [28,29].
angle [28,29]. The obtained
The obtained and Dare
β and Dβvalues values
listedare
in listed
Table in1,
Table 1,the
where where the N-doped
N-doped NiO NSs NiO NSs
have have relatively
relatively largersizes
larger grain grainthan
sizesthose
than those
of theof the non-doped
non-doped NSs.
NSs. Therefore,
Therefore, it can beitestimated
can be estimated that N-doping
that N-doping can increase can
theincrease the crystallinity
crystallinity of NiO NSs. The of NiO NSs.
Scherrer
The Scherrer
equation equationapplicable
is generally is generally forapplicable
spherical for spherical
particles; particles;
it has it hasbecause
limitations limitations
many because
factorsmany
may
factors maytocontribute
contribute to peak broadening
peak broadening in the XRD in the XRD
patterns. Forpatterns.
example, Forthe
example, the deposition
deposition and growthand of
growth of materials on substrates may produce crystallographic strain due to residual
materials on substrates may produce crystallographic strain due to residual stress. Herein, assuming stress. Herein,
assuming
the the same circumstance
same circumstance for N-doped for N-doped and non-doped
and non-doped NiO NSs,NiO NSs, we investigated
we investigated only their only their
relative
relative crystallinities.
crystallinities.

Figure 4.
Figure XRD results
4. XRD results of
of N-doped
N-doped and
and non-doped
non-doped NiO
NiO NSs.
NSs.

Table 1.
Table Structural crystal
1. Structural crystal parameters
parameters of
of N-doped
N-doped and
and non-doped
non-doped NiO
NiO NSs.
NSs.

Sample
Sample β
β (Deg)
(Deg) D D(nm)
(nm)
N-doped NiO
N-doped NiO
0.65 ± 0.02
0.65 ± 0.02
26.3 ± 0.8
26.3 ± 0.8
Non-doped
Non-doped NiO
NiO 1.42 ±
1.42 ± 0.05
0.05 12.0
12.0± ±0.5
0.5

3.3.
3.3. Chemical
Chemical Characterization
Characterization of
of the
the N-Doped
N-Doped NiO
NiO NSs
NSs
The
The chemical structure of NiO was examined, and
chemical structure of NiO was examined, andN-doping
N-dopingwaswasconfirmed
confirmedusing
usingXPS
XPSanalyses.
analyses.
Both
Both N-doped and non-doped NiO NSs showed the peaks of O 1s and Ni 2p (Figure 5), with two
N-doped and non-doped NiO NSs showed the peaks of O 1s and Ni 2p (Figure 5), with two
split peaks of 2p1/2 (872.1 eV) and 2p3/2 (853.2 eV), and a satellite peak of 2p3/2 (860.1 eV) [30,31]. A
peak of N 1s was only observed in N-doped NiO, which indicates the existence of nitrogen atoms in
N-doped NiO (Figure 5a). The high-resolution N 1s peak of N-doped NiO was deconvoluted into
two peaks corresponding to pyridinic and pyrrolic nitrogen components (398.5 and 400.1 eV,
respectively) [32,33]. The presence of these nitrogen species confirms N-doping on the surface of NiO
Nanomaterials 2017, 7, 313 5 of 9

split peaks of 2p1/2 (872.1 eV) and 2p3/2 (853.2 eV), and a satellite peak of 2p3/2 (860.1 eV) [30,31].
A peak of N 1s was only observed in N-doped NiO, which indicates the existence of nitrogen atoms
in N-doped NiO (Figure 5a). The high-resolution N 1s peak of N-doped NiO was deconvoluted
into two peaks corresponding to pyridinic and pyrrolic nitrogen components (398.5 and 400.1 eV,
respectively) [32,33]. The presence of these nitrogen species confirms N-doping on the surface of
Nanomaterials 2017, 7, 313 5 of 9
NiO NSs.

Figure5.5.XPS
Figure XPSspectra
spectraof
ofN-doped
N-dopedand
andnon-doped
non-dopedNiO
NiONSs:
NSs:(a)
(a)wide
widescan
scanspectra
spectraand
and(b)
(b)NN1s
1sspectra
spectra
of N-doped NiO with deconvoluted peaks.
of N-doped NiO with deconvoluted peaks.

3.4.
3.4.NO
NO22 Sensing
Sensing Performance
Performance of
of the
the N-Doped
N-Doped NiO
NiO NSs
NSs Nanostructure
Nanostructure
In
In order
order to elucidate the
to elucidate the NO
NO2 2sensing
sensingperformance
performance of of
thethe synthesized
synthesized NiONiO nanostructures,
nanostructures, gas
gas sensing tests were performed at 200 ◦ C by exposing to various concentrations of NO ,
sensing tests were performed at 200 °C by exposing to various concentrations of NO2, from 1 to28
from
ppm.1 Here,
to 8 ppm. Here, the time
the exposing exposing times.was
was 125 NO125 s. NO
2 was 2 wasinto
injected injected into the measurement
the measurement chamberchamber
(200 °C)
(200 ◦ C) with N . For a quantitative examination, the responsivity (RS) and sensitivity (k) were
with N2. For a quantitative
2 examination, the responsivity (RS) and sensitivity (k) were investigated
investigated
with respectwith
to therespect to the gas concentration,
gas concentration, as defined inasEquations
defined in(2)Equations
and (3): (2) and (3):

R −−RR
Ratm
RSRS(%)( %=) = atm GG × ×100100 (2)
(2)
RR atm
atm
  RS
( )
−1 −1 RSmax
k ppm == Cmax
k ppm (3)
(3)
CGG
where Ratm is the resistance of the sensors measured under air circumstance and RG is the resistance
whereNO
when Ratmgas
is the resistance
is injected of the
with the carrier
sensorsgas.measured
The value underof kair circumstance
was obtained from andtheRGslope
is theofresistance
the best
2
when NO 2 gas is injected with the carrier gas. The value of k was obtained from the slope of the best
linear fitting line in the plots of maximum responsivity (RSmax ) versus NO2 concentration (CG ).
linearthat
Note fitting line
Ratm wasin the plots ofas
measured maximum
13.5 kΩ.responsivity
Figure 6a shows (RSmax) that
versus
RSNO 2 concentration (CG). Note
increased when the sensor
that R atm was measured as 13.5 kΩ. Figure 6a shows that RS increased when the sensor was exposed
was exposed to NO2 because RG decreases due to the p-type semiconducting characteristic of NiO,
to NOthe
where 2 because RG decreases
Ni2+ vacancies due totothe
contribute thep-type semiconducting
hole-conduction characteristic
[34]. After of NiO,
NO2 disposal, where
RS was the Ni2+
reinstated
vacancies
to its initialcontribute to the hole-conduction
stage condition, which represents [34]. After NO
reversible 2 disposal, RS was reinstated to its initial
adsorption and desorption of NO2 on the
stage condition, which represents reversible adsorption
surface of NiO. The N-doped NiO-NS-based sensor exhibited a two-fold and desorption of NO 2 on the surface of NiO.
higher RS than that of
the non-doped device, which can also be confirmed by its two-fold higher the
The N-doped NiO-NS-based sensor exhibited a two-fold higher RS than that of non-doped
k value in Figuredevice,
6b.
which can also be confirmed by its two-fold higher k value in Figure
Thus, there is a linear relationship between responsivity and NO2 concentration in both types of 6b. Thus, there is a linear
relationship
sensors. Hence,between responsivity and
the NiO-NS-based device 2 concentration in both types of sensors. Hence, the NiO-
NOcan be used as quantitative high-precision gas sensors to
NS-based device can
measure NO2 concentrations. be used as quantitative high-precision gas sensors to measure NO2
concentrations.
Note that other reducing gases such as H2 S, NH3 , and H2 are also applicable to N-doped NiO
NS gas Note that other
sensors. reducing
Because gases such
the sensing as H2S, NH
behaviors 3, and H2 are also applicable to N-doped NiO NS
of these gases show negative responsivities with
gas sensors. Because the sensing behaviors of
increasing values of RG [24], selective sensing with the reducing these gases showgasesnegative
and NOresponsivities with
2 is possible when
increasing
the values ofgas
NiO-NS-based [24], selective
RGsensors. However,sensingthewith the reducing
absolute values of gases and NO2 isfor
responsivities possible when the
such reducing
NiO-NS-based gas sensors. However, the absolute values of responsivities for such reducing gases
were still low (less than 50%). Therefore, it is further required to develop an innovative n-type
semiconducting material, which is highly sensitive toward the reducing gases.
Nanomaterials 2017, 7, 313 6 of 9

gases were still low (less than 50%). Therefore, it is further required to develop an innovative n-type
semiconducting
Nanomaterials 2017, 7,material,
313 which is highly sensitive toward the reducing gases. 6 of 9

Figure 6. NO
Figure 6. sensing performance
NO22 sensing performance ofof N-doped
N-doped and
and non-doped
non-doped NiO
NiO NSs:
NSs: (a)
(a) responsivity
responsivity to
to various
various
gas concentrations and (b) sensitivity plots.
gas concentrations and (b) sensitivity plots.

Even though
Even thoughNONOcan
canbe
beconsidered
consideredforfor use
use with
with this
this gasgas sensor,
sensor, direct
direct use use is limited
is limited because
because NO
NO reacts
reacts wellwell
withwith O2 and
O2 and produces
produces NONO 2 easily under a workingtemperature
temperatureofof200 ◦
200 °C. In this case,
2 easily under a working C. In
we kept
we kept the
the working
working temperature
temperature at 200 ◦°C
at 200 when degassing
C when degassing NO NO22 after sensing in order to remove remove
and adsorbed
residual and NO22. Even though the measurement was performed by co-injecting N22 gas,
adsorbed NO
the circumstances
the circumstancesunder
undervacuum
vacuumwere
were not
not ideal.
ideal. Therefore,
Therefore, NONO cancan be reacted
be reacted withwith residual
residual 2 at
O2 atOthis
this high
high working
working temperature,
temperature, andprecise
and the the precise amount
amount of NO of2 NO
then2 then becomes
becomes hardhard to control.
to control.

3.5.
3.5. N-Doping
N-Doping Effect
Effect on
on the
the NiO
NiO NSs
NSs
The
The enhanced
enhanced NONO22 sensing
sensingperformance
performanceofofthetheN-doped
N-dopedNiO NiOdevice
device is is
because
becauseof of
thethe
increase in
increase
p-type conductivity (p+ -type) and the decrease in material resistance by nitrogen doping. Generally,
in p-type conductivity (p -type) and the decrease in material resistance by nitrogen doping.
+

in non-doped NiO, electrical conduction occurs via the hole via

hopping of Ni 2+ vacancies,2+where each
Generally, in non-doped NiO, electrical conduction occurs the hole hopping of Ni vacancies,
vacancy contributes two holes for conduction associated with a p-type semiconducting
where each vacancy contributes two holes for conduction associated with a p-type semiconducting characteristic.
Moreover, oxygen vacancies act as shallow donors, which are responsible
characteristic. Moreover, oxygen vacancies act as shallow donors, which are responsible for n-type conductivity.
for n-type
Therefore, the NO
conductivity. 2 molecules
Therefore, the NOadsorbed to the adsorbed
2 molecules NiO NS surfaces
to the NiO(NO2NS(ads)) accept(NO
surfaces electrons from
2 (ads)) the
accept
NiO surface, and this results in the generation of holes (h+ ) as per Equation (4):
electrons from the NiO surface, and this results in the generation of holes (h ) as per Equation (4):
+

2 (2 (gas
NO
NO gas ) →
)→NO
NO2 (2 (ads
ads ) )
(4)
(4)
NO
NO ( ads
2 (2ads )→) →NO −−
( ads) )++ hh++ ..
2 2(ads
NO

When
When NO NO22 isis adsorbed
adsorbed on on the
the N-doped
N-doped NiONiO surface,
surface, holes
holes are
are generated
generated on on the
the surface
surface by
by an
an
electron
electron transfer
transfer mechanism
mechanism to to the
the NO NO22 molecules. Then, the
molecules. Then, the holes
holes on
on the
the N-doped
N-doped NiO NiO surfaces
surfaces are
are
transferred to the
thenon-doped
non-dopedNiO NiOsurface
surface (p-type). This hole-transfer at pthe + –p heterojunction
transferred to (p-type). This hole-transfer at the +–pp heterojunction leads
leads to a decrease in resistance of the NiO backbone, which carries charges
to a decrease in resistance of the NiO backbone, which carries charges between the two electrodes between the two
electrodes [35,36]. Without such heterojunctions, the generated holes are
[35,36]. Without such heterojunctions, the generated holes are likely to accumulate on the NiOlikely to accumulate on
the NiO surface, causing relatively low responsivity owing to the suppression of
surface, causing relatively low responsivity owing to the suppression of further adsorption of NO further adsorption of2
NO +
2 molecules.
molecules. Therefore,
Therefore, the pthe
+–p p –p heterojunctions
heterojunctions can relieve
can relieve the amassed
the amassed holesholes
and and
can can promote
promote the
the continuous adsorption of
continuous adsorption of NO2, which NO 2 , which results in the high responsivity and sensitivity of the
results in the high responsivity and sensitivity of the sensors.sensors.
Therefore,
Therefore, the
the synergetic
synergetic effect
effect of
of the
the p-type
p-type semiconducting
semiconducting property
property of
of NiO
NiO andand the
the p-type
p-type doping
doping
of
of N
N increased
increased thethe performance
performance of of thethe NO
NO22 sensing.
sensing.

3.6. Repetitive and Saturate Responses of the N-Doped NiO-NSs-Based NO2 Sensor
Furthermore, in order to examine the stability of the N-doped NiO-nased gas sensor, a repetitive
NO2 gas sensing test was performed at a specific NO2 gas concentration of 4 ppm. The NO2 gas flow
was controlled by sequentially turning on (125 s) and turning off (250 s) and the test was done at 200
°C. As shown in Figure 7a, the synthesized gas sensor exhibited stable reversibility of the gas sensing
characteristics under repetitive NO2 exposure conditions, supporting its potential application in NO2
sensors, where cycle-to-cycle variation can be successfully removed. For every cycle, the N-doped
Nanomaterials 2017, 7, 313 7 of 9

3.6. Repetitive and Saturate Responses of the N-Doped NiO-NSs-Based NO2 Sensor
Furthermore, in order to examine the stability of the N-doped NiO-nased gas sensor, a repetitive
NO2 gas sensing test was performed at a specific NO2 gas concentration of 4 ppm. The NO2 gas flow
was controlled by sequentially turning on (125 s) and turning off (250 s) and the test was done at 200 ◦ C.
As shown 2017,
Nanomaterials in Figure
7, 313 7a, the synthesized gas sensor exhibited stable reversibility of the gas sensing 7 of 9
characteristics under repetitive NO2 exposure conditions, supporting its potential application in NO2
NiO-based
sensors, where sensor showed highly
cycle-to-cycle amplified
variation canresponsivity
be successfully (resistance
removed. change) uponcycle,
For every NO2 exposure and
the N-doped
fully recovered
NiO-based signals
sensor showedin the absence
highly amplified with good repetitive
of NO2 responsivity (resistance switching
change)behaviors.
upon NO2With high
exposure
sensitivity, highly stable,
and fully recovered andinrepetitive
signals the absence gas of
sensing performance
NO2 with was observed,
good repetitive which
switching suggestsWith
behaviors. that
the
highpresented
sensitivity,N-doped NiO and
highly stable, nanostructure-based
repetitive gas sensing device has great was
performance potential for applications
observed, which suggests in
quantitatively
that the presented reliable sensorsNiO
N-doped to precisely measure NO2device
nanostructure-based gas. has great potential for applications in
Additionally,
quantitatively the N-doped
reliable sensors toNiO-based sensor showed
precisely measure NO2 gas. stable saturate responses for all different
concentrations
Additionally, of the 2, as shown
NON-doped in Figure
NiO-based sensor7b.showed
After stable
certainsaturate
injection times, for
responses theallvalues of
different
responsivities
concentrationsexhibited
of NO2 , assteady-state
shown in Figure behaviors, which
7b. After confirms
certain thattimes,
injection the developed
the values sensor can give
of responsivities
reproducible responsesbehaviors,
exhibited steady-state for detecting which . For the saturate
NO2confirms response, the
that the developed valuecan
sensor of give
ksat (Equation (3))
reproducible
was calculated
responses as 90.13NO
for detecting ppm 2 . −1
Forby linear-fitting
the saturate (root
response, mean
the square
value of k= 0.96).
sat This
(Equation result
(3)) wasshows that
calculated N-as
doped
90.13 ppm −1 by linear-fitting
NiO-NS-based gas sensors
(root meanare highly
squaresensitive toward
= 0.96). This resultNO 2 gas.
shows Note
that that previous
N-doped work
NiO-NS-based
using the non-doped
gas sensors NiO NStoward
are highly sensitive on a graphene
NO2 gas. Notesubstrate showed work
that previous k = 32.4
usingppmthe −1 . Because NiO
non-doped the
measurement
NS on a graphene circumstance
substratewas kept at
showed k =a 32.4
working − 1
ppmtemperature
. Because of the200 °C, even after
measurement the gas sensing
circumstance was
by NO
kept at 2a injection, all residual of
working temperature and ◦ C, even after
200adsorbed gasesthecould be fully
gas sensing byremoved from all
NO2 injection, theresidual
NiO NSs.and
Therefore,
adsorbed gases the device
couldcan exhibit
be fully stable responses
removed from the NiOfor long-term cycle. It
NSs. Therefore, is device
the noted that the N-doped
can exhibit stable
NiO-based
responses for gaslong-term
sensor showed
cycle. Itnegligible
is noted thatchange on repetitive
the N-doped NiO-basedand saturate
gas sensor responses after one
showed negligible
month.
change on repetitive and saturate responses after one month.

Figure 7.
Figure (a)Repetitive
7. (a) Repetitive and
and (b)
(b) saturate
saturate responses
responses of
of the
the N-doped
N-doped NiO-NS-based
NiO-NS-based NO
NO22 sensors.
sensors.

4. Conclusions
4. Conclusions
NiO has
NiO has been
been widely
widely used
used in
in chemical
chemical sensing
sensing applications,
applications, because
because itit has
has an
an excellent
excellent p-type
p-type
semiconducting property and high chemical stability. Here, in order to develop highly
semiconducting property and high chemical stability. Here, in order to develop highly sensitive and sensitive and
stable NO22 sensors, we successfully fabricated three-dimensional porous N-doped NiO NSs by aa
stable NO sensors, we successfully fabricated three-dimensional porous N-doped NiO NSs by
simple and
simple and effective
effective hydrothermal
hydrothermal technique.
technique. N-doping
N-dopingof ofthis
thisnovel
novelNiONiO NS NS led
led to
to significantly
significantly
enhanced NO sensing performance with a two-fold higher responsivity and
enhanced NO22sensing performance with a two-fold higher responsivity and sensitivity comparedsensitivity compared to
to non-doped NiO +
non-doped NiO NSNS nanostructure.
nanostructure. ThisThis
waswas achieved
achieved by constructing
by constructing p –p
+ p heterojunctions
–p heterojunctions at the
at the N-
N-doped
doped NiONiO sites.
sites. TheThe novel
novel N-doped
N-doped NiONiO nanostructure-based
nanostructure-based device
device exhibited
exhibited highhigh sensitivity
sensitivity and
and stability with good repetitive gas sensing performance. Hence, it is a candidate
stability with good repetitive gas sensing performance. Hence, it is a candidate of choice for of choice for
quantitatively reliable
quantitatively reliable high-precision
high-precision gas
gas sensors
sensors for
for the
the measurement
measurement of of NO gas.
NO2 gas.
Acknowledgments: This work was supported by the National Research Foundation (NRF) of Korea, a grant
Acknowledgments: This work was supported by the National Research Foundation (NRF) of Korea, a grant
funded by the Ministry of Science, ICT and Future Planning (2015R1A2A2A04003160 and 2016M3A7B4021149).
funded by the Ministry of Science, ICT and Future Planning (2015R1A2A2A04003160 and 2016M3A7B4021149).

Author Contributions: Wonoh Lee and Seung Hyun Hur designed the research project. Van Hoang Luan,
Huynh Ngoc Tien, and Seung Hyun Hur conceived and designed the experiments; Van Hoang Luan and Huynh
Ngoc Tien performed the experiments and analyzed the data; Van Hoang Luan, Jong Hun Han, and Wonoh Lee
wrote the paper; all authors discussed and commented on the manuscript.
Nanomaterials 2017, 7, 313 8 of 9

Author Contributions: Wonoh Lee and Seung Hyun Hur designed the research project. Van Hoang Luan,
Huynh Ngoc Tien, and Seung Hyun Hur conceived and designed the experiments; Van Hoang Luan and
Huynh Ngoc Tien performed the experiments and analyzed the data; Van Hoang Luan, Jong Hun Han,
and Wonoh Lee wrote the paper; all authors discussed and commented on the manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

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