Solid State Sciences 82 (2018) 84–91

Contents lists available at ScienceDirect

Solid State Sciences

journal homepage: www.elsevier.com/locate/ssscie

Study of the effect of stress/strain of mesoporous Al-doped ZnO thin films on T

thermoelectric properties
Min-Hee Honga, Haryeong Choia, Dong Il Shimb, Hyung Hee Chob, Jiwan Kimc, Hyung-Ho Parka,∗
a
Department of Materials Science and Engineering, Yonsei University, Seoul 30722, Republic of Korea
b
School of Mechanical Engineering, Yonsei University, Seoul 30722, Republic of Korea
c
Department of Advanced Materials Engineering, Kyonggi University, 154-42 Gwanggyosan-ro, Suwon-si, Gyeonggi-do, Republic of Korea

A R T I C LE I N FO A B S T R A C T

Keywords: In this study, effects of induced stress and strain on the thermoelectric properties of mesoporous ZnO thin films
Mesoporous structure with various Al doping concentrations were investigated. With Al doping in ZnO structure, the hexagonal
Al-doped ZnO thin films wurtzite structure of ZnO was distorted owing to an ionic size difference between Al and Zn. With an increase in
Strain/stress Al concentration to 4 at%, thermal conductivity unexpectedly decreased from 1.70 to 1.24 W/mK owing to an
Williamson–Hall analysis
increase in the tensile strain, and electrical conductivity increased from 4 S/cm to 15 S/cm owing to an increase
Thermoelectric
in the carrier concentration. Based on this study, the relationship between the induced strain owing to lattice
distortion and thermoelectric properties was investigated. Thus, 4 at% Al-doped mesoporous ZnO demonstrated
best enhanced thermoelectric properties.

1. Introduction structure was formed. The as-synthesized mesoporous structure could

Thermoelectricity is a phenomenon of conversion of heat to useful
electricity when a temperature gradient occurs in thermoelectric ma-
terials. Thermoelectricity can be a promising candidate for application
in next-generation green energy techniques because it can use waste
heat and does not create harmful by-products. However, thermoelectric
devices have limitations in commercialization owing to low thermo-
electric property. Thermoelectric property is defined as a figure-of-
merit (ZT) expressed as S2σT/κ, (S: Seebeck coefficient, σ: electrical
conductivity, κ: thermal conductivity, T: absolute temperature). It is
evident from the above equation that high electrical conductivity, high
Seebeck coefficient, and low thermal conductivity are essential to im-
prove thermoelectric properties. Therefore, in this study, a mesoporous
structure with pores of size 2–50 nm was introduced into ZnO thin film
to reduce the thermal conductivity. A porous structure has low thermal
conductivity because phonons are scattered at each pore [1]. Therefore,
researches about porous structure to improve thermoelectric properties
has been carried out [2,3].
The mesoporous structure was first synthesized at Mobile [4]. In this
work, the evaporation-induced self-assembly (EISA) process was
adopted to synthesize the mesoporous structure. An organic surfactant,
which was used as the evaporated solvent, had a micellar structure over
critical micelle concentration. Moreover, the synthesized micellar
structure was decomposed via an annealing process and a pore
reduce the lattice thermal conductivity because each pore acted as a
phonon scattering center. However, as this pore structure scattered not
only phonons but also electrons, the improvement of thermoelectric
property was limited. Therefore, to improve the thermoelectric prop-
erties, it is important to control the thermal conductivity and electrical
conductivity independently. By employing a doping process, the elec-
trical conductivity could be selectively increased owing to the carrier
concentration increasing. In this study, ZnO was used because it has
high thermal stability and it is easy to control the electrical conductivity
by easy doping into Group III elements (Al, Ga, In, etc.). It is a wide
band-gap n-type semiconductor. Therefore, it could be used as a pho-
tovoltaic device [5,6], solar cell [7–9], gas sensor [10–13], and ther-
moelectric device [14–16]. ZnO could be synthesized using various
processes such as sputtering [17,18], atomic layer deposition [19–21],
pulsed laser deposition [22–24], and sol-gel method [25–27]. Further-
more, group III elements such as Al, Ga, and In were doped into the ZnO
structure to improve its electrical and optical properties [28–30]. In this
study, ZnO thin films were synthesized with mesoporous structure by
using the sol-gel method followed by the EISA process. Therefore, the
selective increase in electrical conductivity by doping Al into the me-
soporous ZnO structure was investigated.
When Al was doped into a ZnO structure, the electrical conductivity
increased following to an increase in the carrier concentration [31].
Further, the ZnO lattice was also distorted owing to the difference

∗
Corresponding author.
E-mail address: hhpark@yonsei.ac.kr (H.-H. Park).

https://doi.org/10.1016/j.solidstatesciences.2018.05.010
Received 14 February 2018; Accepted 19 May 2018
Available online 21 May 2018
1293-2558/ © 2018 Elsevier Masson SAS. All rights reserved.
M.-H. Hong et al. Solid State Sciences 82 (2018) 84–91

between the ionic radii of Al3+(0.054 nm) and Zn2+(0.074 nm) [32].
The thermoelectric properties could be controlled using the induced
stress and strain [33–35]. Therefore, in this study, the effects of the
change in electrical conductivity and the induction of strain/stress
owing to Al doping on the thermoelectric properties of the ZnO thin
film were investigated. The change in induced strain and stress ac-
cording to the concentration of Al doping was analyzed by using Wil-
liamson–Hall analysis (W–H analysis). The W–H analysis was composed
of three models: uniform deformation model (UDM) for analyzing the
induced strain of thin films, uniform stress deformation model (USDM)
for analyzing the induced strain and stress, and uniform deformation
energy density model (UDEDM) for analyzing the correlation between
the energy density and strain/stress. In this study, all three models were
applied. Moreover, the effects of induced stress/strain and lattice dis-
tortion on the thermoelectric properties were studied for various Al
doping concentrations.

2. Experimental detail

Mesoporous Al-doped ZnO thin films were synthesized as follows.

First, Brij-S10 block copolymer (C58H118O21, Aldrich, MW 711) was
dissolved in n-PrOH. After stirring for 1 h, zinc acetate dihydrate [Zn
(CH3COO)2•H2O], monoethanolamine (MEA), and aluminum nitrate
nonahydrate [Al(NO3)•9H2O] were added to the solution. In this work,
the molar ratio n-propanol: zinc acetate dihydrate: MEA: Brij-S10 was
34.5: 1: 1: 0.05. Further, the atomic ratio of Zn and Al precursors was
varied from 0 to 4 at%. When Al was doped with a concentration of
more than 4 at%, the distortion of the ZnO structure was too large and
the hexagonal wurtzite structure was destroyed. Therefore, in this
study, Al was doped in the mesoporous ZnO thin films up to the con-
centration of 4 at%. After aging for 1 h, the solution was spin-coated
onto SiO2/Si substrate at 3000 rpm for 30 s at room temperature. SiO2/
Si substrate was used in this experiment because SiO2 is amorphous,
which does not affect the thermoelectric properties and induced strain/
stress. SiO2/Si substrate was sonicated with methanol, ethanol, and
deionized water for 15 min each. Before annealing, the spin-coated
films were pre-baked 300 °C for 10 min to pyrolyze the ZnO precursor
Fig. 1. (a) XRD patterns and (b) lattice parameter of Al-doped mesoporous ZnO
and remove the residual organics. After annealing at 450 °C for 4 h at a thin films with various Al concentration.
heating rate of 1 °C/min, Al-doped mesoporous ZnO thin films could be
synthesized. The low heating rate (1 °C/min) slowly collapsed the pore
structure followed by minimized rapid crystallization and grain growth
[36]. In order to investigate the pore structure of the mesoporous Al-
doped ZnO thin films, grazing-incidence small-angle X-ray scattering
(GISAXS) was used at the 3C beam line (λ = 1.54 Å and Δλ/
λ = 2 × 10−4) of Pohang Light Source (PLS) in Korea [37]. The por-
osity behavior was measured using an ellipsometer (Gatan, L117C,
632.8 nm He-Ne lasers) and Lorentz–Lorenz equation. The cross-sec-
tional thickness of ZnO thin film was investigated using scanning
electron microscopy (SEM, JEOL, Japan). The thermal conductivity of
thin films was measured by 3ω-method [38]. The 3ω-method is a
measurement method for determining the thermal conductivities of
bulk material and thin layers. When the heat is released to the sample
surface in accordance with the frequency, the voltage and current
changes are measured with temperature change. Thereafter, the tem-
perature difference between both ends of the sample is measured to
calculate the thermal conductivity. The electrical properties including
carrier concentration, mobility, and resistivity were measured using a
Hall effect measurement system (HMS-3000, Ecopia). The Seebeck
coefficients and electrical resistivity of the mesoporous ZnO thin films
Fig. 2. Estimated induced strain of Al-doped mesoporous ZnO thin films with
were determined by measuring the Seebeck voltage from 50 °C to
various Al concentration using UDM.
230 °C with an 30° interval.

3. Results and discussion doping concentrations. Furthermore, lattice distortion and stress/strain
of the hexagonal wurtzite structure owing to the difference between the
In this study, X-ray diffraction (XRD) was performed to analyze the ionic radii of Al and Zn were analyzed using XRD. As shown in Fig. 1(a),
change in crystallinity of the ZnO structure according to various Al all the samples had the same hexagonal wurtzite structure regardless of

85
M.-H. Hong et al. Solid State Sciences 82 (2018) 84–91

Fig. 3. Estimated (a) induced strain and (b) stress of Al-doped mesoporous ZnO
thin films with various Al concentration using USDM.

the Al doping concentration; diffraction peaks at 2θ of approximately

31.8°, 33.4°, and 36.2° were indexed as 100, 002, and 101, respectively
(JCPDS card No. 36–1451). With the increase in Al doping concentra-
tion, the intensity of the XRD peak decreased owing to difference ionic
radii of the Al3+ and Zn2+ i.e., 0.054 nm and 0.074 nm. With the in-
crease in Al doping concentration, the intensity of the XRD peak de-
creased due to a distortion of hexagonal wurtzite structure owing to a
difference in the ionic radii of the Al3+ and Zn2+ i.e., 0.054 nm and
0.074 nm. In addition, trivalent cation doping also inhibited gain
growth of ZnO structure [39,40]. Therefore, stress/strain was induced
in ZnO structure and ZnO structure was distorted.
In order to analyze the lattice distortion according to the con-
centration of Al doping, lattice parameters were calculated using the
XRD pattern in Fig. 1(a) and the results are shown in Fig. 1(b). Lattice
parameters (a- and c-axes) were calculated as follows [41]:
λ
a=
3 sin θ100 (1) Fig. 4. Estimated (a) induced strain, (b) stress, and (c) energy density of Al-
doped mesoporous ZnO thin films with various Al concentration using UDEDM.
λ
c=
sin θ002 (2)
the application of uniform tensile strain, the XRD peak was shifted,
where λ is the wavelength of CuK α1 radiation. As shown in Fig. 1(b), the whereas it was broadened with the application of non-uniform strain
lattice parameters (a, c, c/a) had similar values regardless of the Al [43]. In this study, there was no change in the lattice parameter and the
doping concentration. As the lattice parameter depends on the position XRD peak was broadened; thus, it can be concluded that non-uniform
of the XRD peak, a change in the lattice parameter indicates that uni- tensile strain was induced in the ZnO thin film by Al doping. The
form strain is induced in the structure [42]. When strain/stress was change in the induced strain/stress and energy density according to Al
induced in the structure, XRD peaks were shifted or broadened. With

86
M.-H. Hong et al. Solid State Sciences 82 (2018) 84–91

Fig. 5. GISAXS patterns of Al-doped mesoporous ZnO thin films with various Al concentration.

kλ
Dv =
βhkl cos θ (3)

where Dv is the volume-weighted crystallite size, λ is the wavelength of

CuK α1 radiation, k is the shape factor (0.9), and βhkl is the instrumental
corrected integral breadth of the reflection. Furthermore, the induced
strain can be calculated using the following equation, which is derived
from the Scherrer equation:

βhkl
ε=
tan θ (4)

where ε is the induced strain of thin films.

Generally, the W–H analysis is divided into three models: UDM,
USDM, and UDEDM. By applying these three models, the strain, stress,
and energy density of the thin films could be calculated. First, in the
UDM, it is implicit that a uniform strain is induced in all directions of
the materials.
The UDM equation could be derived as follows by rearranging Eqs.
(1) and (2):
Fig. 6. Porosity behavior of Al-doped mesoporous ZnO thin films with various
Al concentration.
kλ
βhkl cos θ = ⎛ ⎞ + (4ε sin θ)
⎜ ⎟

doping concentration could be calculated using W–H analysis. The
broadening of the XRD peak could be attributed to both the decrease in
the crystallite size and the increase in the tensile strain. By using W–H
analysis, it is possible to distinguish between the crystallite size and
induced strain because the crystallite size depends on 1 whereas the
cos θ
induced strain depends on tan θ . The crystallite size can be calculated
using the Scherrer equation as follows:
⎝ Dv ⎠ (5)
The tensile strain change of (100), (002), and (101) according to Al
doping concentration was calculated using UDM and the results are
shown in Fig. 2. As shown in Fig. 2, an increase in the Al doping con-
centration induced an increase in strain. Moreover, in the case of Al
doping concentration of 4 at%, the strain increased rapidly. As the
smaller Al3+ (0.054 nm) substituted the Zn2+ (0.074 nm) ion, the ZnO
structure was distorted and the tensile strain also increased. However,

87
M.-H. Hong et al. Solid State Sciences 82 (2018) 84–91

Fig. 7. Cross-sectional SEM images of Al-doped mesoporous ZnO thin films with various Al concentration.

the result calculated using UDM has a limitation in this mesoporous 1

kλ ⎛ 2u ⎞ 2 ⎞
system because the UDM assumes uniform strain in all crystal direc- βhkl cos θ = ⎛ ⎞ + ⎜4 sin θ ⎛
Yhkl ⎠ ⎟
⎜ ⎟

tions. As shown in Fig. 1(b), it can be concluded that uniform strain was
not induced as Al was doped in mesoporous ZnO thin films because the
lattice parameter did not change. Therefore, the UDM has a limitation
for application to this system. However, as USDM and UDEDM assume
non-uniform strain in the structure, these models are suitable for this
system.
From USDM, the strain could be calculated using Hooke's law,
which indicates linear proportionality between the strain and stress as
σ= Yε , (σ: stress, Y: Young's modulus). Hooke's law has limitation in
that it is valid for significantly small strain. As it was supposed that a
small strain was induced in Al-doped mesoporous ZnO thin films, the
USDM could be applied. USDM can be defined as
kλ 4σ sin θ ⎞
βhkl cos θ = ⎛ ⎞ + ⎛ ⎜ ⎟
⎝D⎠ ⎝ (8)
⎝ ⎠
The change in energy density according to various Al doping con-
centrations and the change in strain/stress derived from Hooke's law
were calculated using Eq. (6) and the results are shown in Fig. 4. In all
the models, the strain tended to increase with the increase in Al doping
concentration. This tendency was due to the increase in tensile strain.
As Al3+ substituted the Zn2+ ion, the crystallinity and grain growth of
the ZnO structure were inhibited and consequently, tensile strain was
induced in the Al-doped mesoporous ZnO thin films.
In this study, the induced strain/stress and energy density could be
calculated using UDM, USDM, and UDEDM. Among these models,
UDEDM is the most suitable model for mesoporous ZnO. In the case of
UDM, the strain was uniform in all the crystallographic directions.

⎝D⎠ ⎝ Yhkl ⎠ (6) However, the XRD peak was not shifted with the increase in the sur-
factant concentration whereas the peak was broadened. Therefore,
In a hexagonal system, the Young's modulus (Yhkl ) [44] is related to UDM is not suitable for this system. USDM and UDEDM are based on
elastic compliances as follows: Hooke's law and these models are valid for small values of strain.
Between the USDM and UDEDM, it is implicit in the UDEDM that
2 crystals are homogeneous and isotropic. Therefore, in this study,
(h + 2k )2 al 2
⎡h2 +
⎣ 3
+ ( ) ⎤⎦
c UDEDM is the most suitable model because all the XRD peaks followed
Yhkl = 2
(h + 2k )2 al 4 (h + 2k )2 al 2 a Gaussian function.
(
s11 h2 + 3 ) + s33 ( )
c
+ (2s13 + s44 ) h2 + ( 3 )( )
c The change in the pore structure according to the Al doping con-
(7) centration was analyzed using GISAXS and the results are shown in
Fig. 5. When a regular structure is formed in materials, GISAXS is used
where s11, s13, s33, and s44 are the elastic compliances of ZnO and their to analyze it as a 2D image and shape pattern. In this study, GISAXS was
values are 7.858 × 10−12 , − 2.206 × 10−12 , 6.940 × 10−12 , and used to analyze the ordered pore structure. Generally, in the sol-gel
− 2.206 × 10−12 m2N−1, respectively [44]. The stress and strain were process, it is difficult to synthesize a pore structure with ZnO. In the
calculated using Hooke's law for each plane and the results are shown in ZnO system, the formation of Zn-O bonds happens faster than in the
Fig. 3(a) and (b), respectively. As observed in Fig. 2, the tensile strain SiO2 and TiO2 systems owing to the high reactivity of the Zn ion pre-
and stress increased with the increase in Al doping concentration. cursor [46–48]. Moreover, the crystallization of ZnO occurs at the low
The energy density (u) could be calculated from the UDEDM. The temperature of approximately 300 °C, and it is difficult to maintain the
(ε 2Y )
strain and stress were calculated using u= 2hkl , which was derived ordered pore structure. Therefore, the pore structure could collapse
from Hooke's Law. In the UDEDM, it is implicit that crystals have an owing to the crystallization and grain growth of ZnO. Therefore, when
isotropic nature and are homogeneous [45]. Further, similar to USDM, compared with mesoporous SiO2 and TiO2, the GISAXS wing pattern of
it is also valid for small strain values. mesoporous ZnO exhibited a relatively low intensity owing to poor pore
The UDEDM can be modified as the following equation: arrangement. However, as shown in Fig. 5, GISAXS wing patterns were

88
M.-H. Hong et al. Solid State Sciences 82 (2018) 84–91

(a) (b)
24
ZnO
2.5 22
Thermal conductivity (W/mK)

ZnO+0.01Al
20 ZnO+0.02Al

Conductivity(/ cm)
18 ZnO+0.04Al
2.0
16
14
1.5 12
10
8
1.0 6
4
2
0.5
0
ZnO ZnO+0.01Al ZnO+0.02Al ZnO+0.04Al 320 340 360 380 400 420 440 460 480
Temperature (K)

(c) (d)
19 -1
2.0x10 5.0x10 -40
14 ZnO

Seebeck Coefficient( V/K)

-50
)

ZnO+0.01Al
-3

-1
4.0x10
Carrier Concentration (cm

Hall Mobility (cm V s )

19 ZnO+0.02Al
2 -1 -1

1.5x10 12
-60 ZnO+0.04Al
Resistivity ( cm)

-1
10 3.0x10 -70
1.0x10
19 Concentration
Mobility -80
8 2.0x10
-1
Resistivity

18
-90
5.0x10 6
-1
1.0x10
-100
4
-110
ZnO ZnO+0.01Al ZnO+0.02Al ZnO+0.04Al 320 340 360 380 400 420 440 460 480
Samples Temperature (K)
Fig. 8. (a) Thermal conductivity, (b) electrical conductivity, (c) Hall measurement result, and (d) Seebeck coefficient of Al-doped mesoporous ZnO thin films with
various Al concentration.

observed and corresponded to the formation of ordered mesoporous
ZnO. Further, the intensity of patterns slightly increased with the in-
crease in Al doping concentration. This slight increase in the pattern
intensity was due to the difference between the ionic radii of Al3+ and
Zn2+ [32] because the ordering of pores could be maintained by doped
Al, which inhibited the grain growth of ZnO as shown in Fig. 1(a).
The porosity behavior for various Al doping concentrations was
analyzed using ellipsometry and the results are shown in Fig. 6. In this
study, the porosity of mesoporous Al-doped ZnO thin films was calcu-
lated by using the Lorentz–Lorenz equation [49].
n2f − 1
n2f + 2
1 − Fp =
ns2 − 1
ns2 + 2
where Fp is the pore volume fraction, nf is the refractive index of the
films, and ns is the refractive index of the structure. With the increase in
Al doping concentration, the porosity slightly increased owing to an
increase in the pore arrangement as shown in Fig. 5. Similar to the
previous study [50], the porosity increased from 33.0% to 37.4% with
an increase in the Al doping concentration up to 2 at% and slightly
increased to 38.4% with 4 at% of Al doping. The thickness of the films
was taken from the cross-sectional SEM images (given as Fig. 7) as 125,
137, 149, and 151 nm for ZnO and Al-doped ZnO with 1, 2, and 4 at% of
Al, respectively. These changs in the thickness were well matched with
the changes in the porosity according to the Al-doping, for example,
33.0% for ZnO thin film and 34.8, 37.4, and 38.4% for Al-doped ZnO
with 1, 2, and 4 at% of Al, respectively. These results also confirmed the
important role of Al dopant as an inhibitor on the grain growth of ZnO
and maintainer of pore ordering in mesoporous ZnO thin films.
Fig. 8 shows the change in thermoelectric properties according to
the Al doping concentration. The thermal and electrical conductivities
and Seebeck coefficient of the mesoporous ZnO thin films were strongly
affected by Al doping. In this study, the aforementioned thermoelectric
properties were also influenced by porosity because when the porosity
increases, both thermal conductivity and electrical conductivity de-
crease, and the Seebeck coefficient increases [51]. However as men-
tioned above, the porosity increased by only 1% with an increase in Al
(9) doping concentration from 2 to 4 at%. Thus, the effect of change of
porosity was neglected when considering the change in the thermo-
electric properties of ZnO films between 2 and 4 at% Al doping. As
shown in Fig. 8(a), the thermal conductivity decreased with the in-
crease in Al doping concentration. When Al was doped in the ZnO
structure, hexagonal wurtzite structure was distorted owing to induced
tensile strain because the smaller Al ion substituted the Zn ion.
Therefore, the thermal conductivity decreased from 1.70 to 1.24 W/mK
with the increase in Al doping concentration, especially from 1.57 to
1.24 W/mK for 2 to 4 at% Al doping. Thus, it can be concluded that this

89
M.-H. Hong et al.
decrease in the thermal conductivity was induced by the increase in
phonon scattering owing to the increased lattice tensile strain in ZnO.
Moreover, as shown in Fig. 8(b), the electrical conductivity of Al-doped
mesoporous ZnO thin films increased by more than three times when
compared with the pristine ZnO thin film owing to the increased carrier
concentration. In order to analyze the carrier concentration and mo-
bility behavior depending on the Al doping concentration, resistivity
was analyzed using the Hall effect measurement and the results are
shown in Fig. 8(c). When Al was doped in the mesoporous ZnO struc-
ture, the carrier concentration increased and mobility decreased.
However, with the increase in Al doping concentration, the mobility
decreased owing to the increased lattice tensile strain. Therefore, the
electrical conductivity was saturated above 2 at% of Al doping con-
centration in ZnO thin films as shown in Fig. 8(b). As shown in
Fig. 8(d), the Seebeck coefficient had a negative value owing to the n-
type semiconductor property of ZnO. As the Al concentration increased,
the absolute value of Seebeck coefficient decreased because the elec-
trical conductivity and Seebeck coefficient were inversely proportional
to each other. However, the change in Seebeck coefficient from 2 to 4 at
% of Al doping concentration was also strongly dependent on the en-
hanced lattice tensile strain as in the case of the thermal and electrical
conductivities. Using the above analyses, it can be concluded that,
when tensile strain is applied to the lattice of thermoelectric materials,
it has a greater effect on the thermal conductivity than on the electrical
conductivity and Seebeck coefficient owing to strongly enhanced
phonon scattering.
4. Conclusion
In this study, mesoporous Al-doped ZnO thin films were synthesized
using the sol-gel method followed by the EISA process. Accordingly, it
was confirmed that the strain induced by lattice distortion of Al-doped
mesoporous ZnO affects the thermoelectric properties. As Al was doped
into the ZnO structure, the hexagonal wurtzite structure was distorted
owing to a difference in ionic radii, tensile strain was induced, and the
overall thermal conductivity decreased. Moreover, the electrical con-
ductivity increased and the absolute value of Seebeck coefficient in-
creased owing to an increase in the carrier concentration.
Consequently, it can be concluded that Al doping in ZnO induces en-
hanced the thermoelectric property. In this study, 4 at% Al-doped me-
soporous ZnO thin films showed the most enhanced thermoelectric
properties.
Acknowledgements
This work was supported by the National Research Foundation of
Korea grant funded by the Korea government (MSIP) (No.
2015R1A2A1A15054541). This work was supported by the Center for
Advanced Meta-Materials (CAMM) funded by the Ministry of Science,
ICT and Future Planning as Global Frontier Project (CAMM-No. NRF-
2014M3A6B3063716). Experiments at PLS were supported in part by
MEST and POSTECH. This work was supported by the Korea Institute of
Energy Technology Evaluation and Planning (KETEP) and the Ministry
of Trade, Industry & Energy (MOTIE) of the Republic of Korea (No.
20163030013980).
References
[1] V.G. Parale, K.-Y. Lee, H.-H. Park, Flexible and transparent silica aerogels: an
overview, J. Kor. Chem. Soc. 54 (2017) 184–199.
[2] M. Ohtaki, R. Hayashi, K. Araki, Thermoelectric properties of sintered ZnO in-
corporating nanovid structure: influence of the size and number density of nano-
voids, Proc 2006 Int Conf Thermoelectrics, 2006, pp. 112–116.
[3] M. Kashiwagi, S. Hirata, K. Harada, Y. Zheng, K. Miyazaki, M. Yahiro, C. Adachi,
Enhanced figure of merit of a porous thin film of bismuth antimony telluride, Appl.
Phys. Lett. 98 (2011) 023114 (1–3).
[4] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Ordered meso-
porous molecular sieves synthesized by a liquid-crystal template mechanism,
90
Solid State Sciences 82 (2018) 84–91
Nature 359 (1992) 710–712.
[5] Q. Zhang, C.S. Dandeneau, X. Zhou, C. Cao, ZnO nanostructures for dye-sensitized
solar cells, Adv. Mater. 21 (2009) 4087–4108.
[6] A.B. Djurisic, X. Liu, Y.H. Leung, Zinc oxide films and nanomaterials for photo-
voltaic applications, Phys. Status Solidi RRL 8 (2014) 123–132.
[7] H. Ra, K. Choi, J. Kim, Y. Hahn, Y. Im, Fabrication of ZnO nanowires using na-
noscale spacer lithography for gas sensors, Small 4 (2008) 1105–1109.
[8] J.A. Anta, E. Guillent, T.-Z. Ramon, ZnO-based dye-sensitized solar cells, J. Phys.
Chem. C 116 (2012) 11413–11425.
[9] S.H. Ko, D. Lee, H.W. Kang, K.H. Nam, J.Y. Yeo, S.J. Hong, C.P. Grigoropoulos,
H.J. Sung, Nanoforest of hydrothermally grown hierarchical ZnO nanowires for a
high efficiency dye-sensitized solar cell, Nano Lett. 11 (2011) 666–671.
[10] L. Znaidi, G.J.A.A. Soler Illia, S. Benyahia, C. Sanchez, A.V. Kanaev, Oriented ZnO
thin films synthesis by sol–gel process for laser application, Thin Solid Films 428
(2003) 257–262.
[11] M.-W. Ahn, K.-S. Park, J.-H. Heo, J.-G. Park, D.-W. Kim, K.-J. Choi, J.-H. Lee, S.-
H. Hong, Gas sensing properties of defect-controlled ZnO-nanowire gas sensor,
Appl. Phys. Lett. 93 (2008) 263103 (1–3).
[12] J. Guo, J. Zhang, M. Zhu, D. Ju, H. Xu, B. Cao, High-performance gas sensor based
on ZnO nanowires functionalized by Au nanoparticles, Sensor. Actuator. B 199
(2014) 339–345.
[13] D. An, Y. Li, X. Lian, Y. Zou, G. Deng, Synthesis of porous ZnO structure for gas
sensor and photocatalytic applications, Colloid. Surface. Physicochem. Eng. Aspect.
447 (2014) 81–87.
[14] K.P. Ong, D.J. Singh, P. Wu, Analysis of the thermoelectric properties of n-type ZnO,
Phys. Rev. B 83 (2011) 115110(1–5).
[15] D.-B. Zhang, B.-P. Zhang, D.-S. Ye, Y.-C. Liu, S. Li, Enhanced Al/Ni co-doping and
power factor in textured ZnO thermoelectric ceramics prepared by hydrothermal
synthesis and spark plasma sintering, J. Alloy. Comp. 656 (2016) 784–792.
[16] J. Loureiro, N. Neves, R. Barros, T. Mateus, R. Santos, S. Filonovich, S. Reparaz,
C.M. Sotomayor-Torres, F. Wyczisk, L. Divay, R. Martins, L. Ferreira, Transparent
aluminium zinc oxide thin films with enhanced thermoelectric properties, J. Mater.
Chem. 2 (2014) 6649–6655.
[17] S.S. Wilson, J.P. Bosco, Y. Tolstova, D.O. Scanlon, G.W. Watson, H.A. Atwater,
Interface stoichiometry control to improve device voltage and modify band align-
ment in ZnO/Cu2O heterojunction solar cells, Energy Environ. Sci. 7 (2014)
3606–3610.
[18] M. Mickan, U. Helmersson, H. Rinnert, J. Ghanbaja, D. Muller, D. Horwat, Room
temperature deposition of homogeneous, highly transparent and conductive Al-
doped ZnO films by reactive high power impulse magnetron sputtering, Sol. Energy
Mater. Sol. Cells 157 (2016) 742–749.
[19] M. Drobek, M. Bechelany, C. Vallicari, A.A. Chaaya, C. Charmette, C. Salvador-
Levehang, P. Miele, A. Julbe, An innovative approach for the preparation of con-
fined ZIF-8 membranes by conversion of ZnO ALD layers, J. Membr. Sci. 475 (2015)
39–46.
[20] K.-M. Kang, Y.-J. Choi, G.Y. Yeom, H.-H. Park, Thickness-dependent growth or-
ientation of F-doped ZnO films formed by atomic layer deposition, J. Vac. Sci.
Technol., A 34 (2016) 01A144 (1–7).
[21] X. Sun, C. Zhou, M. Xie, H. Sun, T. Hu, F. Lu, S.M. Scott, S.M. George, J. Lian,
Synthesis of ZnO quantum dot/graphene nanocomposites by atomic layer deposi-
tion with high lithium storage capacity, J. Chem. 2 (2014) 7319–7326.
[22] H. Agura, A. Suzuki, T. Matsushita, T. Aoki, M. Okuda, Low resistivity transparent
conducting Al-doped ZnO films prepared by pulsed laser deposition, Thin Solid
Films 445 (2003) 263–267.
[23] Y. Liu, J. Lian, Optical and electrical properties of aluminum-doped ZnO thin films
grown by pulsed laser deposition, Appl. Surf. Sci. 253 (2007) 3727–3730.
[24] A.V. Singh, R.M. Mehra, N. Buthrath, A. Wakahara, A. Yoshida, Highly conductive
and transparent aluminum-doped zinc oxide thin films prepared by pulsed laser
deposition in oxygen ambient, J. Appl. Phys. 90 (2001) 5661–5665.
[25] M.M. Ba-Abbad, A.A.H. Kadhum, A.B. Mohamad, M.S. Takriff, K. Sopian, Visible
light photocatalytic activity of Fe3+-doped ZnO nanoparticle prepared via sol–gel
technique, Chemosphere 91 (2013) 1604–1611.
[26] R. Vettumperumal, S. Kalyanaraman, R. Thangavel, Photoconductive UV detectors
based heterostructures of Cd and Mg doped ZnO sol gel thin films, Mater. Chem.
Phys. 145 (2014) 237–242.
[27] X. Zhao, M. Li, X. Lou, Sol–gel assisted hydrothermal synthesis of ZnO micro-
structures: morphology control and photocatalytic activity, Adv. Powder Technol.
25 (2014) 372–378.
[28] A. Mahroug, S. Boudjadar, S. Hamrit, L. Guerbous, Structural, optical and photo-
current properties of undoped and Al-doped ZnO thin films deposited by sol–gel
spin coating technique, Mater. Lett. 134 (2014) 248–251.
[29] G.C. Park, S.M. Hwang, J.H. Lim, J. Joo, Growth behavior and electrical perfor-
mance of Ga-doped ZnO nanorod/p-Si heterojunction diodes prepared using a hy-
drothermal method, Nanoscale 6 (2014) 1840–1847.
[30] S. Ghosh, M. Saha, S.K. De, Tunable surface plasmon resonance and enhanced
electrical conductivity of in doped ZnO colloidal nanocrystals, Nanoscale 6 (2014)
7039–7051.
[31] R. Zamiri, B. Singh, M.S. Belsley, J.M.F. Ferreira, Structural and dielectric proper-
ties of Al-doped ZnO nanostructures, Ceram. Int. 40 (2014) 6031–6036.
[32] K.C. Park, D.Y. Ma, K.H. Kim, The physical properties of Al-doped zinc oxide films
prepared by RF magnetron sputtering, Thin Solid Films 305 (1997) 201–209.
[33] K. Kusagaya, M. Takashiri, Investigation of the effects of compressive and tensile
strain on n-type bismuth telluride and p-type antimony telluride nanocrystalline
thin films for use in flexible thermoelectric generators, J. Alloy. Comp. 653 (2015)
480–485.
[34] R.C. Picu, T. Borca-Tasciuc, M.C. Pavel, Strain and size effects on heat transport in
M.-H. Hong et al.
nanostructures, J. Appl. Phys. 93 (2003) 3535–3539.
[35] R. Ghosh, D. Basak, S. Fujihara, Effect of substrate-induced strain on the structural,
electrical, and optical properties of polycrystalline ZnO thin films, J. Appl. Phys. 96
(2004) 2689–2692.
[36] M.-H. Hong, Ch.-S. Park, H.-H. Park, Study on the enhanced specific surface area of
mesoporous titania by annealing time control: gas sensing property, J.
Microelectron. Packag. Soc. 22 (2015) 21–26.
[37] B. Lee, I. Park, J. Yoon, Structural analysis of block copolymer thin films with
grazing incidence small-angle x-ray scattering, Macromolecules 38 (2005)
4311–4323.
[38] B.-Y. Tsui, C.-C. Yang, K.-L. Fang, Anisotropic thermal conductivity of nanoporous
silica film, IEEE Trans. Electron. Dev. 51 (2004) 20–27.
[39] M. Wang, K.E. Lee, S.H. Hahn, E.J. Kim, S. Kim, J.S. Chung, E.W. Shin, C. Park,
Optical and photoluminescent properties of sol-gel Al-doped ZnO thin films, Mater.
Lett. 61 (2007) 1118–1121.
[40] J. Li, J. Xu, Q. Xu, G. Fang, Preparation and characterization of Al doped ZnO thin
films by sol–gel process, J. Alloy. Comp. 542 (2012) 151–156.
[41] M. Gondal, Q. Drmosh, Z. Yamani, T. Saleh, Synthesis of ZnO2 nanoparticles by
laser ablation in liquid and their annealing transformation into ZnO nanoparticles,
Appl. Surf. Sci. 256 (2009) 298–304.
[42] V.D. Mote, Y. Purushotham, B.N. Dole, Williamson-Hall analysis in estimation of
lattice strain in nanometer-sized ZnO particles, Journal of Theoretical and Applied
Physics 6 (2012) 6 (1-8).
[43] R. Yogamalar, R. Srinivasan, A. Vinu, K. Ariga, A. Chandra Rose, X-ray peak
broadening analysis in ZnO nanoparticles, Solid State Commun. 149 (2009)
91
Solid State Sciences 82 (2018) 84–91
1919–1923.
[44] J.-M. Zhang, Y. Zhang, K.-W. Xu, V. Ji, General compliance transformation relation
and applications for anisotropic hexagonal metals, Solid State Commun. 139 (2006)
87–91.
[45] Y.T. Parabbu, K.V. Rao, V.S.S. Kumar, B.S. Kumari, X-ray analysis by Williamson-
Hall and size-strain plot methods of ZnO nanoparticles with fuel variation, World J.
Nano Sci. Eng. 4 (2014) 21–28.
[46] X. Zi-Qiang, D. Hong, L. Yan, C. Hang, Al-doping effects on structure, electrical and
optical properties of c-axis-orientated ZnO: Al thin films, Mater. Sci. Semicond.
Process. 9 (2006) 132–135.
[47] G.J.D.A.A. Soler-Illia, C. Sanchez, B. Lebeau, J. Patarin, Chemical strategies to de-
sign textured Materials: from microporous and mesoporous oxides to nanonetworks
and hierarchical structures, Chem. Rev. 102 (2002) 4093–4138.
[48] P. Yang, D. Zhao, D.I. Margolese, B.F. Chmelka, G.D. Stucky, Block copolymer
templating syntheses of mesoporous metal oxides with large ordering lengths and
semicrystalline framework, Chem. Mater. 11 (1999) 2813–2826.
[49] M.R. Baklanov, K.P. Mogilnikov, V.G. Polovinkin, F.N. Dultsev, Determination of
pore size distribution in thin films by ellipsometric porosimetry, J. Vac. Sci.
Technol. B 18 (2000) 1385–1391.
[50] M.-H. Hong, C.-S. Park, W.-S. Seo, Y.S. Lim, J.-K. Kim, H.-H. Park, Thermoelectric
properties of Al-Doped mesoporous ZnO thin films, J. Nanomater. 2013 (2013) 1–6
ID 131537.
[51] T.-J. Ha, H.-H. Park, S.-Y. Jung, S.-J. Yoon, J.-S. Kim, H.W. Jang, Effect of porosity
on the Seebeck coefficient of mesoporous TiO2 thin films, Thin Solid Films 518
(2010) 7196–7198.