1
Scientific RepoRts | 6:19187 | DOI: 10.1038/srep19187
www.nature.com/scientificreports
Micro/Nano hierarchical peony-like
Al doped ZnO superhydrophobic
lm: The guiding eect of (100)
preferred seed layer
Yang Li
1,*
, Jingfeng Wang
1,*
, Yi Kong
1
, Jia Zhou
1
, Jinzhu Wu
1
, Gang Wang
1
, Hai Bi
1
,
Xiaohong Wu
1
, Wei Qin
2
& Qingkun Li
3
In this communication, we present a versatile and controllable strategy for formation of
superhydrophobic micro/nano hierarchical Al doped ZnO (AZO) lms with a water contact angle (CA) of
170 ± 4°. This strategy involves a two-step layer-by-layer process employing an atomic layer deposition
(ALD) technique followed by a hydrothermal method, and the resulting novel AZO surface layer consists
of (100) dominant nano-rice-like AZO seed layer (the water CA of 110 ± 4°) covered with micro-peony-
like AZO top. The growth mechanisms and superhydrophobic properties of the hierarchical AZO layer
are discussed. It is believed that the present route holds promise for future success in the design and
development of practical superhydrophobic materials.
Superhydrophobic materials and coatings with water contact angle larger than 150° have been extensively investi-
gated due to their wide applications from housewares to industrial products
1,2
. For instance, solar cell panels, gog-
gles and windows for photoelectronic devices generally demand their surfaces with properties of self-cleaning,
anti-fog and superhydrophobicity
3
. e key points of superhydrophobic states include the surface energy of the
chemical composition and the geometrical rough structure of solid surfaces
4
. Owing to the lower surface energy,
the organic peruorinated materials turn into the most common hydrophobic material, however those organic
coatings are costly and unstable for the application. erefore, increasing attentions are drawn on some inorganic
materials with specic hierarchical rough surfaces
5,6
.
Al-doped ZnO (AZO) materials have attracted considerable attentions owing to their unique optical and
electrical properties, such as wide band gap and high exciton binding energy
7–9
. AZO lm can provide valence
ions and higher carrier mobility, making it a desirable candidate for various photovoltaic and solar cell applica-
tions
10,11
. erefore, the superhydrophobic AZO intelligent materials are potential and promising in the photo-
electric elds.
To fabricate the required superhydrophobic surface roughness of AZO lm, various methods have been pro-
posed in literatures. A two-step layer-by-layer approach were adopted in several research groups
12,13
. AZO seed
layer was deposited on a substance by solution method, sol–gel method, magnetron sputtering methods and
others, which can lower the activation barrier for the following nucleation and enhance the lm adhesive force
with top layer. Micro-nano AZO structures were fabricated subsequently using the hydrothermal method, plasma
etching, and vapor deposition on the seed layer
14,15
. It is worth fabricating the special and micro/nano hierarchical
AZO structure surface, by enhancing the surface roughness, so that superhydrophobic AZO lms materials can
be achieved, without involving the peruorinated material.
In most research works, the surface of ZnO micro-nanorods arrays grown based on (002) preferred seed layer
is still hydrophilic, and thus the uorination method needs to be used for formation of the superhydrophobic sur-
face texture
16
. In contrast, other orientation dominant seed layer tends to induce more complex micro nanostruc-
ture for superhydrophobic surface
17
. In this case, the seed layer obviously plays a subtle guiding role in controlling
1
Department of Chemistry, Harbin Institute of Technology, Harbin, Heilongjiang 150001, PR China.
2
School of
Materials Science and Engineering, Harbin Institute of Technology, Harbin, Heilongjiang 150001, PR China.
3
Key
Laboratory of Electrical Engineering, College of Heilongjiang Province Major Laboratories of Integrated Circuits,
Heilongjiang University
*
These authors contributed equally to this work. Correspondence and requests for materials
should be addressed to X.W. (email: wuxiaohong@hit.edu.cn) or W.Q. (email: qinwei@hit.edu.cn)
Received: 28 June 2015
accepted: 07 December 2015
Published: 12 January 2016
OPEN
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