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1700107 (1 of 8) ©
2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmattechnol.de
Simple and Versatile High Aspect Ratio Nanostructuring
via Zinc Oxide Masking
Agnieszka Gwiazda,* Anna Rumyantseva, Anisha Gokarna, Komla Nomenyo,
Clotaire Chevalier-César, and Gilles Lérondel*
DOI: 10.1002/admt.201700107
form of a thin film can be easily struc-
tured by wet etching wherein a photoresist
pattern is used or by direct photodissolu-
tion
[15]
as has also been recently demon-
strated by Chevalier-César et al.
[16]
and
also by photo-crosslinking.
[17]
At the same
time ZnO has a low pulverization rate.
Therefore, structuration using dry etching
technique becomes extremely difficult. A
few articles report application of ZnO as a
sacrificial layer in dry etching, namely, in
chemically roughened ZnO thin films for
glass texturing
[18]
or ZnO hydrothermal
nanorods which have been used in the
fabrication of GaN micropillars and nano-
pillars on LED wafers.
[19]
With a low pul-
verization rate, ZnO is expected to be a
good hard mask material for dry etching,
however, its application as a mask has not
been reported so far.
Nowadays, material science presents
a growing need of material structuring
at micro and nanoscale. Controlled and precise structuring
becomes crucial for numerous applications, such as micro- and
nanoelectronics,
[20]
photonics,
[21]
and MicroElectroMechanical
Systems (MEMS).
[22]
These requirements have led to the devel-
opment of various methods of dry plasma-assisted etching,
such as conventional reactive-ion etching (RIE) or inductively
coupled plasma (ICP-RIE) as well as deep reactive-ion etching
(DRIE) techniques such as the cryogenic or Bosch process.
The DRIE processes allow one to obtain a higher aspect ratio
structures but require specialized equipment. Most of these
techniques are well developed by now but are often limited
to silicon
[23,24]
only, while there is a great interest to structure
any kind of material. Micro and nanostructuring provides new
properties to the material allowing creation of multifunctional
surfaces that can have potential applications in many areas.
Structuring or roughening of the surfaces improves the wetting
properties of the materials.
[25,26]
This proves to be an advantage
for biomedical devices.
[27,28]
For some applications, well-defined
and ordered structures are required, as it allows creation of
super-repellent materials for self-cleaning
[29]
and antireflective
surfaces for solar cells.
[30]
For structuration of any kind of materials, the choice of the
mask plays a crucial role as far as plasma-etching process is
concerned. The mask should offer a high selectivity and at the
same time its deposition and structuring should be simple to
implement. Soft masks such as the photoresists require very
This article reports a new universal masking technique based on ZnO.
This technique combines two main properties of the material. ZnO has an
extremely low pulverization rate making the material well adapted for dry
etching, and second, it can be easily chemically dissolved in solution making
the material well suited for masking. Using ZnO as a mask on silicon, one
can achieve selectivity as high as 60. This allows one to etch holes through
a 30 μm thick wafer. Sub-100 nm features are obtained using interferential
lithography as a masking technique. There is no intrinsic limitation in this
technique excepting the texture of the initial ZnO thin film. To demonstrate
the versatility of this technique, it has been successively applied to other
materials such as Si
3
N
4
, TiO
2
, and an organic resist (SU-8) with a selectivity
of up to 15:1, 5:1, and 35:1, respectively. The technique reported in this article
opens the way to universal masking which is extremely important for the
development of multifunctional nanostructured surfaces in any kind of mate-
rials with direct applications in antireflection coating, hydrophobicity, and
hydrophilicity to only name a few.
A. Gwiazda, Dr. A. Rumyantseva, Dr. A. Gokarna, Dr. K. Nomenyo,
Dr. C. Chevalier-César, Prof. G. Lérondel
Laboratoire de Nanotechnologie et d’Instrumentation Optique
Institut Charles Delaunay
CNRS UMR 6281
Université de Technologie de Troyes
12 Rue Marie Curie, CS 42060, 10004 Troyes, France
E-mail: agnieszka.gwiazda@utt.fr; gilles.lerondel@utt.fr
Laser Interference Lithography
1. Introduction
Zinc oxide (ZnO) is a multifunctional material because of its
unique physical and chemical properties. As a semiconductor
with a wide electronic bandgap (3.36–3.4 eV) and large exciton
binding energy (60 meV), it finds various applications in opto-
electronic devices such as UV lasers,
[1]
UV photodetectors,
[2]
and light-emitting diodes (LEDs).
[3]
The piezo and pyroelectric
properties of ZnO allow one to use it in converters,
[4]
energy
generators,
[5]
and sensor
[6,7]
applications while its photocatalytic
properties serve largely in production of hydrogen.
[8]
ZnO pre-
sents a very rich variety of structures which can be obtained by
several methods including chemical bath deposition (CBD),
[9,10]
hydrothermal synthesis,
[11]
sol-gel process,
[12]
as well as chem-
ical vapor deposition (CVD),
[13]
pulsed laser deposition (PLD),
and physical vapor deposition (PVD) technique.
[14]
ZnO in the
Adv. Mater. Technol. 2017, 1700107