nanomaterials
Article
Effect of Aluminum Doping Ratios on the Properties of
Aluminum-Doped Zinc Oxide Films Deposited by Mist
Chemical Vapor Deposition Method Applying
for Photocatalysis
Htet Su Wai and Chaoyang Li *






Citation: Wai, H.S.; Li, C. Effect of
Aluminum Doping Ratios on the
Properties of Aluminum-Doped Zinc
Oxide Films Deposited by Mist
Chemical Vapor Deposition Method
Applying for Photocatalysis.
Nanomaterials 2022, 12, 195. https://
doi.org/10.3390/nano12020195
Academic Editors: Ki-Hyun Kim and
Deepak Kukkar
Received: 9 December 2021
Accepted: 3 January 2022
Published: 7 January 2022
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Nanomaterials 2022, 12, 195. https://doi.org/10.3390/nano12020195
School of Systems Engineering, Kochi University of Technology, Kami, Kochi 782-8502, Japan;
246004f@gs.kochi-tech.ac.jp
* Correspondence: li.chaoyang@kochi-tech.ac.jp; Tel.: +81-887-57-2106
Abstract: Aluminum-doped zinc oxide film was deposited on a glass substrate by mist chemical
vapor deposition method. The influence of different aluminum doping ratios on the structural and
optical properties of zinc oxide film was investigated. The XRD results revealed that the diffraction
peak of (101) crystal plane was the dominant peak for the deposited AZO films with the Al doping
ratios increasing from 1 wt % to 3 wt %. It was found that the variation of AZO film structures
was strongly dependent on the Al/Zn ratios. The intertwined nanosheet structures were obtained
when Zn/O ratios were greater than Al/O ratios with the deposition temperature of 400 ◦ C. The
optical transmittance of all AZO films was greater than 80% in the visible region. The AZO film
deposited with Al doping ratio of 2 wt % showed the highest photocatalytic efficiency between
the wavelength of 475 nm and 700 nm, with the high first-order reaction rate of 0.004 min−1 under
ultraviolet radiation. The mechanism of the AZO film influenced by aluminum doping ratio during
mist chemical vapor deposition process was revealed.
Keywords: aluminum doping ratio; zinc oxide film; photocatalytic property; mist chemical vapor deposition
1. Introduction
In the last decade, the photocatalytic process has been mainly involved in the degra-
dation of chemical pollutants and hazardous industrial waste [1,2]. In 1972, Fujishima et al.
observed the unique properties of semiconductor-based photocatalysts on photoelectro-
chemical water splitting, such as nontoxicity, photosensitivity, and high oxidizing effi-
ciency [3–7]. Since then, many popular metal oxides have been applied as semiconductor
photocatalysts, including magnesium oxide, titanium dioxide (TiO2 ), silver oxide, copper
(II) oxide and zinc oxide (ZnO), due to their excellent physical and chemical proper-
ties [8–13]. Among them, ZnO has also emerged as a potential semiconductor photocatalyst
due to its promising properties, such as a wide bandgap (3.37 eV) at room temperature, large
exciton binding energy (60 meV), super-hydrophilicity, high redox potential, higher surface
reactivity, durability, and low cost [14–16]. Moreover, it is well established that the main
factor in determining the photocatalytic efficiency of ZnO is the photo-excitation process,
which involves excitation, diffusion, and surface transfer of photogenerated charged carri-
ers [17–19]. However, the faster recombination rate of photogenerated electron-hole pairs
can reduce the photocatalytic efficiency of ZnO. It was reported that the recombination rate
of electron-hole pairs could be reduced by modifying the surface, introducing the defects or
doping with transition metals in ZnO [20–24]. Compared with other methods, aluminum
(Al) doping is expected to be a more efficient method of reducing the electron-hole pairs
recombination rate of ZnO [25–27]. The Al could be doped into ZnO films via different
methods, such as radio frequency magnetron sputtering, sol–gel method, chemical vapor
https://www.mdpi.com/journal/nanomaterials
Nanomaterials 2022, 12, 195 2 of 11

deposition (CVD), atomic layer deposition and spray pyrolysis, et al. [28–30]. However,
there are still issues regarding the controlling of surface morphology, growth direction and
the cost [31–33]. It was reported that mist CVD had advantages on the film deposition such
as high uniformity, high reproducibility, simplicity, easy to control, and low cost [34–37].
In our previous research, we had successfully used the mist CVD method to fabricate
the TiO2 film [38,39]. In this research, we planned to apply the mist CVD method to
synthesize aluminum-doped ZnO (AZO) thin film. The effect of Al doping ratios on the
properties of films was investigated, and the photocatalytic activity of AZO films was
investigated as well.

2. Experiments
2.1. Deposition of AZO Films
AZO thin films (300 nm thick) were fabricated on the glass substrate by the mist
CVD method. A solution of mixed precursor was prepared by dissolving the zinc acetate
(0.04 mol/L) and aluminum acetylacetonate in water and methanol (90 mL:10 mL). The
mist droplets of precursor solution were generated from the solution chamber by ultrasonic
transducer at 2.4 MHz, and the droplets transferred to the reaction chamber by nitrogen gas
serving as both carrier gas (2.5 L/min) and dilution gas (4.5 L/min). The substrate was set
up in the fine channel of the reaction chamber, which was heated and kept at 400 ◦ C during
the deposition process. In order to investigate the effect of Al doping ratios on structural
and optical properties of AZO films, the doping ratios of Al were set as 1 wt % to 5 wt %
for comparison. The deposition conditions are summarized in Table 1.

Table 1. Deposition conditions of AZO films by the mist CVD method.

Deposition Parameter Condition

Solute Zinc acetate, Aluminum acetylacetonate
Solvent Methanol, H2 O
Concentration (mol/L) 0.04
Al doping ratio (wt %) 1, 2, 3, 4, 5
Deposition temperature (◦ C) 400
Carrier gas, flow rate (L/min) 2.5
Dilution gas, flow rate (L/min) 4.5

2.2. Photodegradation Process

The photocatalytic measurements of AZO films were carried out in a glass beaker at
room temperature. The methyl red (MR) solution with concentration of 1 × 10−5 mol/L and
volume of 70 mL was prepared, and stirred by wrapping the aluminum foil to prevent the
light for 30 min prior to the irradiation. The deposited AZO films with different Al doping
ratios were submerged in the MR solution individually and irradiated under an ultraviolet
light with a wavelength of 254 nm for 5 h during the measurement process. In order to
analyze the degradation rate as the function of reaction time, the irradiated solution was
taken out at each 1 h interval.

2.3. Characterization
The thicknesses of AZO films were measured by spectroscopic ellipsometry (WVASE32,
J.A. Woollam, Co., Inc., Lincoln, CA, USA). The morphologies of AZO films were evaluated
by field emission scanning electron microscopy (FE-SEM, SU-8020, Hitachi, Tokyo, Japan)
and atomic force microscope (AFM, Nano-R2, Pacific Nanotechnology, Santa Clara, CA,
USA). The structural properties of AZO thin films were investigated by grazing incidence
X-ray diffraction (GIXRD, ATX-G, Rigaku, Tokyo, Japan). A UV-visible spectrophotometer
(U-4100, Hitachi, Tokyo, Japan was used to evaluate the optical properties of AZO films, as
well as the absorption spectra of MR solution. All of the measurements were carried out at
room temperature.
 Santa Clara, CA, USA)). The structural properties of AZO thin films were investigated by
grazing incidence X-ray diffraction (GIXRD, ATX-G, Rigaku, Tokyo, Japan). A UV-visible
spectrophotometer (U-4100, Hitachi, Tokyo, Japan was used to evaluate the optical prop-
erties of AZO films, as well as the absorption spectra of MR solution. All of the measure-
Nanomaterials 2022, 12, 195 3 of 11
ments were carried out at room temperature.

3. Results and Discussion

3. Results and Discussion
The AFM images of AZO films deposited with different Al doping ratios by the mist
CVD The AFMare
method images of in
shown AZO films1.deposited
Figure with area
The scanning different
was Al 5 ×doping
5 (μm2ratios by observed
). It was the mist
CVD method are shown in Figure 1. The scanning area was 5 × 5 (µm 2 ). It was observed
that the root mean square (RMS) surface roughness of AZO films decreased from 6.4 nm
that
to 3.7the
nmroot mean
as the Al square
doping(RMS) surface roughness
ratio increased of AZO
from 1 wt % to 2films
wt %,decreased from 6.4
then slightly nm to
increased
from 4.6 nm to 9.7 nm as the Al ratios increased from 3 wt % to 5 wt %. The lowestfrom
3.7 nm as the Al doping ratio increased from 1 wt % to 2 wt %, then slightly increased RMS
4.6 nm to 9.7 nm as the Al ratios increased from 3 wt % to 5 wt %. The lowest RMS value of
value of AZO films was obtained at an Al doping ratio of 2 wt %. The RMS values of AZO
AZO films was obtained at an Al doping ratio of 2 wt %. The RMS values of AZO films are
films are summarized in Table 2.
summarized in Table 2.

AFMimages
Figure1.1.AFM
Figure imagesofof
AZOAZO films
films with
with different
different Al Al doping
doping ratios
ratios by the
by the mistmist
CVDCVD method:
method: (a) 1
(a) 1 wt % Al, (b) 2 wt % Al, (c) 3 wt % Al, (d) 4 wt % Al, and (e) 5
wt % Al, (b) 2 wt % Al, (c) 3 wt % Al, (d) 4 wt % Al, and (e) 5 wt % Al. wt % Al.

Table 2.
Table The RMS
2. The RMS roughness
roughness of
of AZO
AZO films.
films.

Al Doping
Al Doping Ratio
Ratio (wt%)
(wt %) RMS
RMS Roughness(nm)
Roughness (nm)
1 1 6.4
6.4
2 2 3.7
3.7
3 4.6
3 4.6
4 8.8
4 5 8.8
9.7
5 9.7
The GIXRD patterns of AZO films deposited with different Al doping ratios by the
mistThe
CVD GIXRD
method patterns of AZO
are shown films 2.
in Figure deposited
The (101)with
peakdifferent
was the Al doping peak
dominant ratiosfor
bythe
the
mist CVD method are shown in Figure 2. The (101) peak was the dominant
AZO films deposited with Al doping ratios of 1 wt % to 3 wt %, which meant that the peak for the
AZO films deposited with Al doping ratios of 1 wt % to 3 wt %, which meant
growth of ZnO film exhibited the highly preferred orientation along the (101) crystal plane. that the
growth of ZnO film
Three diffraction exhibited
peaks the highly
of (100), (002) preferred
and (101) orientation
were observed in thealong
AZOthefilms(101) crystal
deposited
plane.
with an Three diffraction
Al doping ratio peaks
of 1 wtof%.
(100),
The (002)
(100) and
and (101)
(002) were
peaksobserved in the AZO
became weaker whenfilms
the
deposited with an Al doping ratio of 1 wt %. The (100) and (002) peaks
Al doping ratio was increased to 2 wt %, then disappeared when the Al doping ratios became weaker
when
were the Al doping
increased to 3 ratio
wt %.was Noincreased
diffractiontopeaks
2 wt %, thenobserved
were disappeared when
on AZO the when
films Al doping
the
ratios were ratios
Al doping increased
weretoincreased
3 wt %. Noto 4diffraction
wt % and 5peaks
wt %,were observed
indicating thaton
theAZO films films
obtained when
the Alamorphous.
were doping ratios were increased to 4 wt % and 5 wt %, indicating that the obtained
films The
wereaverage
amorphous.
crystallite size along the (101) crystal plane for AZO films was calculated
using Debye–Scherrer’s formula [40]. The crystallite size of AZO films was significantly reduced
from 31.82 nm to 13.56 nm when the Al doping ratio was increased from 1 wt % to 3 wt %.
 The average crystallite size along the (101) crystal plane for AZO films was cal
using Debye–Scherrer’s formula [40]. The crystallite size of AZO films was signi
Nanomaterials 2022, 12, 195 reduced from 31.82 nm to 13.56 nm when the Al doping ratio was increased 4 of 11 from
to 3 wt %.

Figure 2. GIXRD patterns of AZO films with different Al ratios by the mist CVD method.
Figure 2. GIXRD patterns of AZO films with different Al ratios by the mist CVD method.
Using the texture coefficient (TC) (hkl) formula [41], the preferred orientation of the
(hkl) Using
plane fortheAZOtexture coefficient
film could (TC) (hkl)
be determined. Theformula
TC values[41], the films
of AZO preferred orientation
calculated
(hkl) plane for AZO film could be determined. The TC values of AZOthe
based on the XRD data from Al ratios of 1 wt % to 3 wt % are shown in Table 3. From films cal
TC value results, it was confirmed that the TC value of (002) peak only existed at an Al
based on the XRD data from Al ratios of 1 wt % to 3 wt % are shown in Table 3. Fr
doping ratio of 1 wt %. The TC value of the (100) peak was significantly reduced when the
TC value
Al ratio wasresults,
increaseditfrom
was1 confirmed
wt % to 3 wt that the TC to
%. Compared value
the TCofvalue
(002)of peak only
(002) and existed a
(100)
doping ratio
orientations, theofTC
1 wt %.ofThe
value (101)TC value
peak of the
was the (100) peak
dominated was significantly
orientation reduced
for all three kinds of w
AZO films, which meant that the preferred growth of AZO films was (101)
Al ratio was increased from 1 wt % to 3 wt %. Compared to the TC value of (002) an crystal plane.
orientations, the TC value
Table 3. Texture coefficient ofAZO
values of (101) peak
films was with
deposited the different
dominated orientation for all thre
Al ratios.
of AZO films, which meant that the preferred growth of AZO films was (101)
Al Doping Ratio (wt %) TC (100) TC (002) TC (101)
plane.
1 2.785 1.542 3
2 0.126 - 0.732
Table 3. Texture
3 coefficient values of AZO films
0.117 deposited
- with different Al
0.654 ratios.

Al Doping Ratio (wt %) TC (100) TC (002) TC (10

Figure 3 shows the SEM images of AZO films deposited with different Al doping
ratios by the mist1 CVD method. It was clearly
2.785 1.542 morphologies
observed that the surface 3
were significantly2 changed with increased Al doping
0.126 ratios. The intertwined
- nanosheet 0.732
structures were observed only at Al doping ratios of 1 wt % and 2 wt %. The length of
3 0.117 - 0.654
the nanosheets were significantly reduced, and the structures were changed into uniform
particles as Al doping ratios increased from 3 wt % to 5 wt %. The reason for the structure
Figure
change might3beshows
becausethe SEM
of the images of variation
corresponding AZO films in thedeposited with ofdifferent
lattice constants ZnO Al
ratios by the mist
films influenced by theCVD method.
Al doping ratios.ItWith
wasthe
clearly
increaseobserved
in Al dopingthat the there
ratios, surface
was morph
much Al 3+ (ionic radius 0.53 Å) substituted into ZnO film instead of Zn2+ (ionic radius
were significantly changed with increased Al doping ratios. The intertwined nan
0.74 Å), which can lead to the structure distortion due to the different ionic radius.
structures were observed only at Al doping ratios of 1 wt % and 2 wt %. The lengt
nanosheets were significantly reduced, and the structures were changed into unifo
ticles as Al doping ratios increased from 3 wt % to 5 wt %. The reason for the st
change might be because of the corresponding variation in the lattice constants
films influenced by the Al doping ratios. With the increase in Al doping ratios, the
much Al3+ (ionic radius 0.53 Å) substituted into ZnO film instead of Zn2+ (ionic rad
Å), which can lead to the structure distortion due to the different ionic radius.
Nanomaterials 2022, 12, x FOR PEER REVIEW 5 of 11
Nanomaterials 2022, 12, 195 5 of 11

FigureFigure
3. SEM images
3. SEM of AZO
images of AZO films with
films withdifferent Aldoping
different Al doping ratios
ratios by by
the the
mistmist
CVDCVD method.
method. (a) 1 wt(a)
%1
wt % Al,
Al,(b)
(b)2 2wtwt % Al, (c) 3 wt % Al, (d) 4 wt % Al, and (e) 5 wt % Al: (1) top view, and (2)
% Al, (c) 3 wt % Al, (d) 4 wt % Al, and (e) 5 wt % Al: (1) top view, and (2) cross-section view). cross-
section view).
EDX measurement was carried out in order to evaluate the elemental composition
of deposited
EDX measurement AZO filmswas with
carrieddifferent
out inAl doping
order ratios bythe
to evaluate theelemental
mist CVDcomposition
method. Theof
variation of the atomic percentages of Al/Zn, Al/O,
deposited AZO films with different Al doping ratios by the mist CVD method. Zn/O, and (Al + Zn)/O are shown
The vari-in
Figure 4. It was found that the atomic ratio of Al/Zn was significantly
ation of the atomic percentages of Al/Zn, Al/O, Zn/O, and (Al+Zn)/O are shown in Figure increased as the Al
ratios were increased from 1 wt % to 5 wt %, which meant that more Al ions were doped
4. It was found that the atomic ratio of Al/Zn was significantly increased as the Al ratios
into ZnO, the maximum value was at Al doping ratio of 3 wt %. The atomic ratios of Al/O
were increased from 1 wt % to 5 wt %, which meant that more Al ions were doped into
and (Al + Zn)/O slightly increased; in contrast, that of Zn/O gradually decreased as the Al
ZnO,ratios
the maximum
were increased valuefromwas1atwtAl%doping ratio
to 5 wt %. Theofatomic
3 wt %. Theofatomic
ratios Zn/O ratios of Al/O
were greater and
than
(Al+Zn)/O slightly
Al/O when theincreased;
Al dopingin contrast,
ratios were that of Zn/O
at 1 wt % andgradually
2 wt %, which decreased
meant as thethe
that AlZn-O
ratios
were bond
increased from 1 wt % to 5 wt %. The atomic ratios of Zn/O
was dominated to form ZnO. When the Al doping ratios increased to 3 wt % and were greater than Al/O
whenfurthermore,
the Al doping ratios were
the atomic ratio ofatAl/O
1 wt was
% and 2 wtthan
greater %, which meantwhich
that of Zn/O, that the Zn-O bond
indicated that
was dominated to form
the Al ions served asZnO. When the
the oxidizing Al to
agent doping
replaceratios
the Znincreased to 3 wt % and
ion sites incorporated further-
to oxygen
more,ions
theto form AZO
atomic ratio and Al1−xwas
of Al/O Ox . greater
However, the that
than atomic ratio ofwhich
of Zn/O, (Al + Zn)/O increased
indicated that the andAl
reached a maximum at 2 wt %, then significantly decreased and
ions served as the oxidizing agent to replace the Zn ion sites incorporated to oxygen ions stayed at nearly level from
3 wt
to form % toand
AZO 5 wtAl %,1−xwhich might be due
Ox. However, to the saturation
the atomic of oxygen ions
ratio of (Al+Zn)/O bonding.
increased and reached
a maximum at 2 wt %, then significantly decreased and stayed at nearly level from 3 wt
% to 5 wt %, which might be due to the saturation of oxygen ions bonding.
Nanomaterials 2022, 12, x FOR PEER REVIEW 6 of 11
Nanomaterials 2022, 12, 195 6 of 11
Nanomaterials 2022, 12, x FOR PEER REVIEW 6 of 11

Figure 4. Variations of Al/Zn, Al/O, Zn/O, and (Al+Zn)/O atomic ratios calculated from EDX analy-
Figure 4.
Figure 4. Variations
sis of AZO Variations ofofAl/Zn,
films deposited Al/Zn, Al/O, Zn/O,
with Al/O, Zn/O,
different
and
and(Al
Al ratios
+ Zn)/Oatomic
(Al+Zn)/O
by
atomic ratios
the mist CVD
ratios calculated from EDX
method. calculated from EDX analy-
sis of AZO films deposited with different Al ratios by the mist CVDmethod.
analysis of AZO films deposited with different Al ratios by the mist CVD method.
The mechanism of growth direction of AZO films deposited with different Al ratios
The mechanism of growth direction of AZO films deposited with different Al ratios
by the mist
The CVD method
mechanism of are shown
growth in schematic
direction of AZOdiagram
films(Figure 5). The growth
deposited of AZO
by the mist CVD method are shown in schematic diagram (Figure 5).withThedifferent
growth ofAl ratios
films
by themainly includes
mist mainly
CVD methodthree stages: (a) in
mist droplets diagram
generation, (b) nucleation, and (c)of AZO
AZO films includesare shown
three stages: schematic
(a) mist droplets (Figure
generation, 5).(b)
The growth
nucleation,
growth
films process. In the first stage, the mixed precursors of zinc acetate (ZA) and aluminum
and (c)mainly
growthincludes
process. In three stages:
the first stage,(a)the
mist
mixeddroplets generation,
precursors (b) nucleation,
of zinc acetate (ZA) and and (c)
acetylacetonate (AA) were prepared in the solution chamber and transformed into mist
growth
aluminum process. In the first
acetylacetonate stage,
(AA) were the mixed precursors
prepared of zinc
in the solution acetate
chamber and(ZA) and aluminum
transformed
droplets
into mist by the ultrasonic
droplets transducer.
by the ultrasonic transducer.
acetylacetonate (AA) were prepared in the solution chamber and transformed into mist
droplets by the ultrasonic transducer.

Figure 5. Growth
Figure 5. Growth model
model of
of AZO
AZO films
films deposited with different
deposited with different Al
Al ratios
ratios by
by the
the mist
mist CVD
CVD method:
method:
(a) mist droplets
droplets generation,
generation, (b)
(b) nucleation,
nucleation, and
and (c)
(c) growth
growth process.
process.

In
In the
the second
second stage,
stage, the
the mist
mist droplets
droplets including
including thethe ZA
ZA andand AAAA were
were transported
transported to to
the reaction
Figure 5. chamber,
Growth in
model which
of AZO the fine
films channel
deposited substrate
with was
differentpreheated
Al and
ratios by kept
the at 400
mist CVD◦ C.method:
the reaction chamber, in which the fine channel substrate was preheated and kept at 400
During the nucleation process, ◦ C, which is greater than the
(a)
°C.mist droplets
During generation,
the nucleation (b)the
process,substrate
nucleation, was (c)
and
the substrate heated
growth
was to 400
heatedprocess.
to 400 °C, which is greater
decomposition temperature ◦
of AA (193of AAC) and ◦
than the decomposition temperature (193ZA
°C)(237
and C).
ZAThe(237decomposed Al ions were
°C). The decomposed Al
much easier
In the to generate
second than
stage, Zn
the ions
mist to bond
droplets with the
includingoxygenthe ions
ZA due
and
ions were much easier to generate than Zn ions to bond with the oxygen ions due to the to
AA the fact
were that the
transported to
decomposition
the
factreaction temperature
chamber, in which
that the decomposition of AA was lower
the fine
temperature than
of channel ZA. Moreover,
substrate
AA was lower thanwas it was already
ZA. preheated reported
Moreover, itandwaskept
al- at 400
that thereported
bondingthat
modetheofbonding
AlO6 could beofconfirmed when the deposition temperature was
°C. During the nucleation process, the substrate was heated to 400 °C, which is greater
ready mode AlO6 could be confirmed when the deposition
temperature
than was greater than
the decomposition 350 °C during
temperature of AAthe mist°C)
(193 deposition
and ZA process
(237 °C).[42].
TheTherefore,
decomposed Al
ions were much easier to generate than Zn ions to bond with the oxygen ions due to the
fact that the decomposition temperature of AA was lower than ZA. Moreover, it was al-
ready reported that the bonding mode of AlO6 could be confirmed when the deposition
Nanomaterials 2022, 12, x FOR PEER REVIEW 7 of 11
Nanomaterials 2022, 12, 195 7 of 11

in this experiment,
greater the Al-O
than 350 ◦ C during thebonds were becoming
mist deposition dominant
process and forming
[42]. Therefore, in thisAl 1−xOx with
experiment,
the increase in Al doping ratios at the growth temperature of 400
the Al-O bonds were becoming dominant and forming Al1−x Ox with the increase°C, resulting in thein
sup-
Al
pression of crystal nucleation of ZnO. ◦
doping ratios at the growth temperature of 400 C, resulting in the suppression of crystal
In the final
nucleation of ZnO.stage, ZnO was formed with the preferential growth in the (101) direction,
whichIn might bestage,
the final due toZnO
its fastest growth
was formed compared
with to the other
the preferential growthgrowth
in the directions [43].
(101) direction,
Therefore,
which thebe
might intertwined
due to its nanosheet structures
fastest growth were formed
compared whengrowth
to the other the Al ratios increased
directions [43].
from 1 wt % to 3 wt %.
Therefore, the intertwined nanosheet structures were formed when the Al ratios increased
fromThe
1 wtoptical
% to 3 transmittance
wt %. of AZO films with different Al doping ratios by the mist
CVDThemethod aretransmittance
optical shown in Figure 6a. The
of AZO transmittance
films of all
with different Al AZO
dopingfilms wasby
ratios more than
the mist
80% in
CVD the visible
method region.inMoreover,
are shown Figure 6a.theTheblue-shift of theof
transmittance absorption edgewas
all AZO films wasmore
observed,
than
which
80% in meant that region.
the visible the energy gaps slightly
Moreover, increased
the blue-shift when
of the the Al ratios
absorption edgewere increased
was observed,
from 1 meant
which wt % tothat
5 wt %.energy gaps slightly increased when the Al ratios were increased
the
from 1 wt % to 5 wt %.

(a) (b)
Figure 6.
Figure 6. (a)
(a) Optical
Optical transmittance
transmittance spectra,
spectra, and
and (b)
(b) Variation of bandgap
Variation of bandgap in
in AZO
AZO films
films deposited
deposited
with different Al ratios by the mist CVD method.
with different Al ratios by the mist CVD method.

The optical
The optical bandgap
bandgapvariations
variationsofof
AZO
AZO film by by
film plotting (αhv)
plotting 2 versus
(αhv) energy
2 versus of pho-
energy of
ton (hv)(hv)
photon withwith
the the
different Al ratios
different areare
Al ratios described
describedin Figure 6 (b).
in Figure 6b. The
The optical
optical bandgaps of
bandgaps of
films were
AZO films were calculated
calculated by
by Tauc’s
Tauc’splot
plotequation
equation[44],
[44],as
asin
inthe
thefollowing;
following;
(αhv)2 = A (hv − Eg) (1)
(αhv)2 = A (hv − Eg ) (1)
where A is the constant, h is Planck’s constant, v is the photon frequency and Eg is the
where
opticalAbandgap.
is the constant, h is Planck’s
The optical bandgapsconstant,
increasedv is the 3.58
from photon
eV frequency
to 3.87 eV and
when Egthe
is the
Al
optical bandgap. The optical bandgaps increased
doping ratios were increased from 1 wt % to 5 wt %. from 3.58 eV to 3.87 eV when the Al
doping ratios
Figure 7awere
showsincreased from 1 wt
the absorption % to of
spectra 5 wt
MR%.solution for AZO films deposited with
different Al doping ratios by the mist CVD method.solution
Figure 7a shows the absorption spectra of MR for AZO that
It was observed filmsthe
deposited with
intensities of
different Al doping ratios by the mist CVD method. It was observed
absorption spectra decreased between 475 nm and 700 nm when the Al ratios were in-that the intensities
of absorption
creased from 1spectra
wt % to decreased
4 wt %, as between
compared475 with
nm and 700 nm when
the original the Al (black
MR solution ratios were
line).
increased from
The obtained 1 wt %
results to 4 wtthat
indicate %, as compared with the
photodegradation originalwas
efficiency MRachieved.
solution (black line).
The lowest
The obtained results indicate that photodegradation efficiency was achieved. The lowest
absorption intensity was obtained at Al doping ratio of 2 wt %. When the Al ratios in-
absorption intensity was obtained at Al doping ratio of 2 wt %. When the Al ratios increased
creased to 5 wt %, the absorption spectrum was slightly higher than the original solution,
to 5 wt %, the absorption spectrum was slightly higher than the original solution, which
which meant that there was no photodegradation efficiency.
meant that there was no photodegradation efficiency.
Nanomaterials 2022, 12, x FOR PEER REVIEW 8 of 11
Nanomaterials 2022, 12, 195 8 of 11

(a) (b)
Figure
Figure 7.
7. (a)
(a) The
The absorption
absorption spectra of MR
spectra of MR solution
solutionfor
forAZO
AZOfilms
filmsdeposited
depositedwith
withdifferent
differentAlAl dop-
doping
ing ratios; and (b) plot of ln (C/Co) versus the reaction
ratios; and (b) plot of ln (C/Co) versus the reaction time. time.

In
In order
order to
tocalculate
calculate the
thedegradation
degradation rate
rate of
ofobtained
obtainedAZOAZOfilms,
films, the
theabsorption
absorption band
band
at
at 520
520 nmnm was
was selected,
selected, which
which corresponds
corresponds to to the
the red
red color
color of
of MR
MR solution.
solution. Based
Based on
on the
the
variations
variations in thethe intensity
intensityofofabsorption
absorptionspectra,
spectra,thethe rates
rates of of photocatalytic
photocatalytic degradation
degradation are
are presented
presented in Figure
in Figure 7b. Langmuir–Hinshelwood
7b. Langmuir–Hinshelwood (L–H)(L–H)
mode mode
[45] [45]
can becanused
be used to de-
to describe
the degradation
scribe kinetickinetic
the degradation of various organicorganic
of various dyes. The adsorption
dyes. rate may
The adsorption be may
rate represented in
be repre-
terms of
sented inthe coverage
terms of the ratio of adsorbed
coverage ratio of reactants
adsorbedon the photocatalyst
reactants surface. The
on the photocatalyst rate of
surface.
reaction,
The rate ofR,reaction,
can be described
R, can beas Equationas(2)
described [46].
Equation (2) [46].
R−
R= = −dC/dt
dC/dt == kkrrθ,
θ, (2)
(2)
where C is the concentration of the reactant, t is the reaction time, kr is the reaction rate
where C is the concentration of the reactant, t is the reaction time, kr is the reaction rate
constant, and θ is the coverage ratio of reactants.
constant, and θ is the coverage ratio of reactants.
According to the adsorption theory, the adsorption capacity and concentration of re-
According to the adsorption theory, the adsorption capacity and concentration of reac-
actant correspond to the coverage ratio of the reactant. In order to determine the adsorp-
tant correspond to the coverage ratio of the reactant. In order to determine the adsorption
tion capacity, the adsorption coefficient of reactant was defined as K. Therefore, the θ can
capacity, the adsorption coefficient of reactant was defined as K. Therefore, the θ can be
be expressed as Equation (3) [45].
expressed as Equation (3) [45].
θ=θ KC/(1 + KC)
= KC/ (1+KC) (3)
(3)
Then, Equation
Then, Equation(3)
(3)can
canbebesubstituted
substituted
toto Equation
Equation (2);(2);
thethe reaction
reaction rate,rate, R can
R can be
be ex-
expressed
pressed as as Equation
Equation (4).(4).

R =R−=dC/dt
−dC/dt==kkr rKC/(1
KC/ (1+KC)
+ KC) (4)
(4)
For pseudo first-order reaction, KC, is smaller than 1 [47], then Equation (4) can be
For pseudo first-order reaction, KC, is smaller than 1 [47], then Equation (4) can be
expressed as,
expressed as,
R=R− = dC/dt
−dC/dt== kkrr KC (5)
(5)
Equation (5)
Equation (5) can
can be
be described
described as
as per
per the
the Integration
Integration Law, as follows;
ln (C) − ln (Co) = kt,
ln (C) − ln (Co) = kt, (6)
(6)
ln (C/Co) = kt
ln (C/Co) = kt
where k is the first-order reaction rate constant.
where k is the
Figure 7b first-order
shows the reaction
plot of lnrate constant.
(C/Co) as a function of UV irradiation time for photo-
Figure 7b shows the plot of ln (C/Co)
catalytic degradation of MR solution for AZO as afilms
function
withofdifferent
UV irradiation timeratios.
Al doping for photo-
The
catalytic
value of Codegradation of MRas
was determined solution for AZO
the original films with
absorbance different
of MR Al doping
solution and the ratios.
value ofTheC
value of Co was determined as the original absorbance of MR solution and the value of
Nanomaterials 2022, 12, 195 9 of 11

C was determined as the absorbance of each AZO film with different Al doping ratios.
According to the Langmuir–Hinshelwood (L–H) mode, the higher value of first-order rate
corresponds to the higher photocatalytic efficiency [48].
In order to calculate the first-order reaction rate constant k, the following equation can
be rewritten from Equation (6).
k = ln (C/Co)/t (7)
According to Equation (7), the calculated first-order reaction rate increased from
0.003 min−1 to 0.004 min−1 when the Al ratios was increased from 1 wt % to 2 wt %, then
decreased from 0.0005 min−1 to 0.0003 min−1 when the Al ratios were increased from
3 wt % to 4 wt %. The highest reaction rate was observed from the AZO film with Al
doping ratio of 2 wt %.

4. Conclusions
The Al was successfully doped into ZnO film with controllable ratios by the mist CVD
method. It was confirmed that the properties of AZO films were significantly influenced
by the Al ratios. The highly preferred orientation of AZO films was along the (101) crystal
plane when the Al doping ratios were increased from 1 wt % to 3 wt %. The best crystallinity
and the lowest surface roughness were obtained at an Al doping ratio of 2 wt %. The crystal
structures of AZO were transformed from intertwined nanosheets to uniform particles as
the Al doping ratios increased. The growth mechanism revealed that Al-O bonds were
enhanced and greater than the Zn-O bond when the Al doping ratios increased at the
deposition temperature of 400 ◦ C during the mist CVD process. The transmittance of all
AZO films was higher than the 80% in the visible region. The AZO film with Al doping
ratio of 2 wt % showed the highest photodegradation efficiency and the highest value of
first-order reaction rate of 0.004 min−1 . The obtained AZO films can be expected to have
applications in environmental purification processes.

Author Contributions: Conceptualization, H.S.W.; methodology, H.S.W.; investigation, H.S.W.; data

analysis, H.S.W.; writing—original draft preparation, H.S.W.; writing—review and editing, C.L.;
visualization, C.L.; supervision, C.L.; project administration, C.L.; funding acquisition, C.L. All
authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: All required data are provided within the manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

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