Microelectronic Engineering 132 (2015) 98–119

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Microelectronic Engineering
journal homepage: www.elsevier.com/locate/mee

Review Article

Nanoimprint technology for patterning functional materials

and its applications
Chen-Chieh Yu, Hsuen-Li Chen ⇑
Department of Materials Science and Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan, ROC

a r t i c l e i n f o a b s t r a c t

Article history: Functional materials including metals, ceramics, plastics, and nanomaterials are now widely adopted in
Received 19 April 2014 modern devices. To facilitate the fabrication of nanostructured functional materials, nanoimprint lithog-
Received in revised form 11 October 2014 raphy (NIL) technology is developed. The nanoimprint technologies for patterning functional materials
Accepted 17 October 2014
are reviewed in this paper. Versatile NIL-based methods have been developed according to the material
Available online 23 October 2014
properties of the target functional materials. Besides the NIL involving dry etching or lift-off process, we
also introduce other NIL-based methods such as the direct NIL, reversal NIL, solid state electrochemical
Keywords:
stamping, nanotransfer printing, sol–gel NIL and many other improved NIL for functional materials. These
Nanoimprint lithography
Reversal nanoimprint lithography
methods demonstrate various advantages. For example, the direct NIL facilitates the direct formation of
Surface plasmon resonance functional metal or plastic nanostructures with a high reproducibility at the centimeter scale, the tem-
Sol–gel process plate stripping method aims to reduce the surface roughness of metal nanostructures to a few-angstrom
Roll-to-roll process scale. Besides, multilayer 3D metal/polymer/ceramic nanostructures can be readily achieved on many
Nanomaterials kinds of substrates by reversal NIL or nanotransfer printing. Moreover, the sol–gel NIL for ceramics,
roll-to-roll process for plastics, and some other NIL-based methods for patterning functional materials
and nanomaterials are introduced. The optical and electrical properties of the nanostructured functional
materials prepared by NIL are discussed. Additionally, the applications of these nanostructured functional
materials are also introduced in this article. Overall, this review aims to inspire next-generation devices
to be developed by NIL with versatile choices of imprinting processes and materials.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction materials can be textured by NIL, and functional devices are

Since the first development in 1995 [1], the nanoimprint lithog-
raphy (NIL) has become one of the advanced patterning methods
for nanofabrication. The idea of NIL is to transfer patterns by press-
ing a designed master mold into resist. While photolithography
suggests the prevention of the mechanical contact between the
mask and resist, NIL is carried out distinctly by the intimate con-
tact between the mold and resist. NIL overwhelms other litho-
graphic processes by its low cost, high throughput, and high
resolution. Versatile micro- and nano-structures have been fabri-
cated using NIL. In the early stage, NIL was mainly carried out on
thermoplastic materials (resist). Since functional materials featur-
ing different structures and patterns have found wide applications
on modern industries, how to fabricate micro- and nano-structures
on functional materials becomes a big issue. NIL for patterning
functional materials is a new branch besides its early development
on the resist based semiconductor process. Various kinds of
⇑ Corresponding author.
E-mail address: hsuenlichen@ntu.edu.tw (H.-L. Chen).
obtained accordingly. Besides, based on the concept of NIL, various
derivative procedures are developed.
Here, we offer a general overview of NIL for functional materi-
als. As it is a rapidly growing research topic, we cannot hope our
review to be comprehensive. However, we will do our best to
describe the major research results and to review a wide cross-sec-
tion of relative literatures. Section 2 describes the NIL for metals.
Various kinds of NIL methods have been developed to texture met-
als. Besides, various morphologies of metallic structures can be
obtained by NIL. These metallic structures demonstrate unique
optical property, and can be applied as functional devices. In Sec-
tion 3, the NIL for ceramics are discussed. Ceramics are materials
with high hardness and mechanical resistivity. These properties
make using NIL to pattern ceramics a challenge. In the review,
we describe some breakthroughs on the NIL for ceramics, and their
further applications. Section 4 describes the NIL for patterning
plastics. Plastic materials become soften at elevated temperatures.
Therefore, the imprinting temperature is a critical issue in NIL for
plastic materials. More importantly, NIL for plastic materials is
compatible with roll-to-roll (R2R) process, and many high-speed

http://dx.doi.org/10.1016/j.mee.2014.10.015
0167-9317/Ó 2014 Elsevier B.V. All rights reserved.
 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119
R2R NIL methods are developed accordingly. In Section 5, NIL for
nanomaterials including carbon nanotubes (CNTs), graphene, and
metallic nanoparticles (NPs) are described. The properties of
nanomaterials largely depend on their dimensions. Nanostructured
nanomaterials open a new field in modern science and technology,
and NIL has been proved as an efficient method to prepare such
patterned nanomaterials with desired critical dimensions.
2. NIL for metals
Metal is a widely used material in daily life and in many indus-
tries. On physical property, metal possesses good electrical and
thermal conductivity. Besides, the ductility and malleability of
metal make it easy to be mechanically drawn into wires or rolled
into sheets. Therefore, metal has found versatile applications.
Metallic nanostructures display distinct properties from their bulk
counterparts. In particular, the plasmonic property of metallic
nanostructures attracts great interests. Surface plasmon is the col-
lective oscillation of free electrons on the interface of metal/vac-
uum (or metal/dielectric). For periodical metal nanostructures,
the incoming photons will get additional momentums from the
periodical structures, and then excite the surface plasmons into
resonance, which is generally known as surface plasmon resonance
(SPR) [2–4]. On the other hand, the resonance of surface plasmons
on metallic nanoparticles (NPs) or other isolated metallic nano-
structures is called localized surface plasmon resonance (LSPR)
for the surface plasmon polaritons do not propagate away from
the NPs surface [5–7]. In this section, we will describe some meth-
ods that employ the NIL to pattern metals, including the lift-off
process, direct NIL, electrochemical NIL, and nanotransfer printing
(also referred as reversal NIL and template stripping in most ways).
Also, we will further discuss the optical, plasmonic, electrical, and
mechanical properties of these metallic structures, and their appli-
cations on real devices.
2.1. NIL involving lift-off process
On electron beam lithography or photolithography, lift-off pro-
cess is widely used to pattern metal structures. The process is car-
ried out by first patterning the photoresist by the exposure of
electron beam or light. After development, the metal films are
deposited on the patterned photoresist. The photoresist (with the
metal films on top) are subsequently removed by solvent, leaving
the metal patterns on the substrates. However, the electron beam
lithography and photolithography are relatively high-cost and
complicated. Additionally, it would be difficult to achieve large-
area fabrication in a short period of time by these lithographic
methods. To increase the throughput, NIL has been developed to
replace the electron beam lithography and photolithography. The
process of conventional NIL is shown in Fig. 1. Because conven-
tional NIL provides the direct patterning of photoresist by mechan-
ical contact, the light or electron beam exposure procedure can be
eliminated. Also, large-area photoresist can be patterned in a single
step, and thus the fabrication time can be greatly reduced. Note
that herein we define the NIL on resist as the conventional NIL,
in order to distinguish from other improved NIL technologies that
will be introduced later. Accordingly, NIL is regarded as an efficient
method for replacing electron beam lithography and photolithog-
raphy, and is suitable for fabricating metallic nanostructures.
Many metallic nanostructures have been fabricated by NIL. The
surface morphologies of metal nanostructures are mainly deter-
mined by the morphologies of the master mold. Metallic lines
and dots have been demonstrated in the early stage [1,8,9]. The
resolution of NIL can reach down to the sub-100-nm scale, and
thus NIL is potential for various applications. Some complicated
99
mold
resist
substrate
(a) (b) (c)
metal
(d) (e)
Fig. 1. Schematic illustration of the conventional NIL involving lift-off process,
including (a) imprinting the mold into resist, (b) demolding, (c) removal of residual
resist by reactive ion etching (RIE), (d) deposition of metal, and (e) removal of resist,
leaving metal patterns on substrate.
metallic nanostructures have been developed by NIL. For example,
circular concentric gratings have been demonstrated with different
periods and line-widths. In previous study, nanoring arrays [10],
circular metallic gratings with a minimum line-width of 80 nm
were obtained [11]. Moreover, because the lift-off patterns are lar-
gely determined by the imprinted resist layer, the property of the
resist layer would affect the final patterns. The air bubbles in the
resist layer would also influence the imprinted patterns. It is found
that the optimized thickness and the imprinting parameters could
eliminate the air bubbles in the resist layer. The solubility of air in
resist layer depends on the process conditions such as temperature
and pressure. Moisture and solvent in resist may participate in the
formation of air bubbles. A pre-bake process for the resist layer and
carrying out the imprinting process under vacuum condition aim
to reduce air bubbles. As demonstrated by Li and co-workers
[11], the pattern duplication in poly(methyl methacrylate) (PMMA)
was uniform in large area when NIL was performed under an opti-
mized imprinting process.
Elliptical Au nanodisks arrays could be fabricated as well [12].
The Au nanodisks were fabricated by the NIL involving lift-off pro-
cess. In the process, a tilted evaporation of Cr was carried out
before using the plasma etching to remove the residual resist layer.
The Cr layer acted as the etching mask that protected the edges of
the resin from being etched and produced an undercut in the side-
walls of the imprinted structures during plasma etching. As a
result, metal nanodisk arrays could be readily fabricated on a glass
wafer by the following lift-off process.
2.2. Direct NIL
In the conventional lift-off process, the metallic structures are
obtained after several steps, including shaping the resist by NIL,
dry etching, metal deposition, and lift-off. Besides using the lift-
off process to pattern metals, a much more convenient way is to
pattern metals directly. Because metals possess a good ductility
and malleability, they are particularly favorable for the direct
forming processes. In 2003, Hirai et al. demonstrated the direct
patterning of fine Au gratings by NIL [13]. To increase the hardness
of a Si mold, a 20-nm-thick Si3N4 film was deposited on the mold
surface by low-pressure chemical vapor deposition (LP-CVD). The
Si mold was pressed to an Au film on a glass substrate at room
temperature through several hundred MPa of pressure. In the
study, they indicated that the substrates were easily fractured dur-
ing imprinting when the area of mold was smaller than that of sub-
strates. Therefore, to eliminate fatal fracture of the sample in
pressing, the form of the sample was well aligned to the mold to
avoid stress concentration at the mold edges. In 2008, Buzzi et al.
used the direct metal NIL to fabricate metal-containing optical
100 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119
devices [14]. In their procedure, they used a lateral confinement (a
ring made by molybdenum alloy) to avoid the stress concentration
at the edges and the excess metal flows on the sides. To carry out
the process, various patterns with lateral dimensions down to
250 nm and aspect ratios of up to 5 were first etched in Si wafers
to prepare Si molds. Next, the Si mold was directly imprinted on
the metal film like Ag or Au. With this configuration, metallic
structures with various shapes and aspect ratios were readily
obtained. This technique was therefore suitable for fabricating
metallic optoelectronic devices with a desired feature size down
to 200 nm. Moreover, A.I.M. Greer et al. performed the direct NIL
to construct nanostructures on Ti surface using a diamond stamp
[15,16]. Ti was widely adopted in biomedical applications such
dental and orthopaedic implants [15–17]. The surface features of
the Ti-based implants would influence the cell adhesion property.
For example, to precisely control the surface morphologies of the
Ti-based implants might help to prevent unwanted cell growth
on temporary implants [15]. However, Ti was a relatively hard
material that was difficult to pattern. Therefore, the diamond mold,
which possessed a greater hardness, would be a suitable choice for
direct NIL on Ti. A.I.M. Greer et al. have successfully transferred
hole arrays (diameter = 200 nm, depth = 50 nm) onto Ti surface
using a diamond mold. Besides, they found that the anodization
of Ti surface would help to reduce the imprinting pressure. The
imprinted trench depth increased ca. 110 nm when performing
direct NIL on the anodized Ti surface, compared to that on the pure
Ti surface (ca. 12 nm) under the same load (100 kg).
Although the direct NIL for metals has been demonstrated, such
process with ultra-high pressure (several hundred MPa) and high
temperature [18] is not desirable because it would damage the
underlying substrates or devices. An improved direct NIL for met-
als reveals a much higher throughput than the previous direct NIL
with large pressures and the one using lift-off process. The
improved direct NIL for metals was first proposed in 2006 by our
group [19]. The direct NIL for metals was based on metal/polymer
bilayer structure, and the procedure is displayed in Fig. 2. To over-
come the ultra-high imprinting pressure, a sharp-tip mold was
used instead of the conventional flat-top one. Because the imprint-
ing pressure would be concentrated at the tips, the applied pres-
sure could be reduced accordingly. Besides, by introducing a soft
(a)
(b)
(c)
Fig. 2. (a) Schematic illustration of the direct NIL by using a soft buffer layer. (b–e) SEM images of (b) a sharp-tip grating Si mold, (c) the imprinted corrugated metal film, (d) a
sharp-tip cone Si mold, and (e) the imprinted perforated metal hole arrays. Reprinted with permission from Ref. [20] (Copyright 2008 Optical Society of America).
polymer layer underneath the metal film, the imprinting process
could be carried out at a temperature below the glass-transition
temperature (Tg) of the polymer. When the processing tempera-
ture was close to Tg, the polymer layer would become soft, and
therefore the metal/polymer bilayer would be deformed simulta-
neously and easily. In the conventional NIL process, the process
temperature was heated to about 20–30 °C above the Tg of resists
to ensure the resist become flowed. However, if the processing
temperature in the improved NIL for metals was much higher than
the Tg of underlying resist layer, the flowing resist would overflow
to the surface of gold films and caused poor pattern quality. This
result indicated that the temperature of the improved direct NIL
for metals must be maintained below the Tg of the underlying
resist layer to avoid pattern distortion. Various morphologies of
metal film could be readily achieved by the improved NIL for met-
als using different shapes of molds and imprint pressures. For
example, a periodical corrugated metal film was obtained using a
sharp grating mold (Fig. 2b and c) [19–21] whereas hole arrays
were fabricated by using a sharp cone mold (Fig. 2d and e) [20].
2.3. Solid state electrochemical stamping
Another way to directly pattern metals is the solid state electro-
chemical stamping proposed by Hsu et al. in 2007 [22]. This
method shows advantages of high reproducibility and high-fidelity
pattern transfer with features down to 50 nm and thicknesses
ranging from 50 to 500 nm. Unlike the direct NIL mentioned above,
the solid state electrochemical stamping process was carried out
by using a stamp made of a superionic conductor (Fig. 3). For
example, the Ag2S was used as the stamp in which the silver ions
were mobile [22,23]. Because the Ag2S demonstrated relatively
low yield strength compared to that of Si, the Ag2S could be pre-
patterned with fine features by a Si mold. After the Ag2S was tex-
tured, this Ag2S stamp was pressed onto the metallic substrate.
Then an electrical bias was applied on the metal substrate (anode)
and an electrode at the back of the stamp (cathode). At the metallic
substrate/stamp interface, an apparent potential drop caused the
oxidation of silver atoms on the metallic substrate and generated
mobile silver ions. These silver ions moved in the lattice of the
superionic conductor (stamp) through some voids and defects
(d)
(e)
 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119
Fig. 3. Schematic illustration of the solid state electrochemical stamping. (a) A bias
was applied between the superionic stamp and the metal substrate, and the stamp
was brought into contact with the metal substrate. (b) The metal substrate was
dissolved and generated mobile ions. (c) The patterns were transferred onto the
metal substrate. Reprinted with permission from Ref. [22] (Copyright 2007
American Chemical Society).
toward the back cathode. This anodic dissolution of the metallic
substrates, assisted by an applied pressure to maintain electrical
contact, progressively promoted the stamp into the substrate,
and generated a negative-replica pattern in the silver substrate.
Depending on different metal substrates to be patterned, the mate-
rial of the stamp should be altered. For example, to apply solid
state electrochemical stamping process on copper substrate, Cu2S
should be used [24]. Additionally, the etching rate typically
increased with the applied bias.
2.4. Nanotransfer printing/reversal imprint/template stripping
2.4.1. Nanotransfer printing
Typically, the concept of conventional NIL or direct NIL for
metal is to transfer patterns by pressing a designed master mold
into target materials. The target materials are deformed during
imprinting process, and their patterns are obtained after demold-
ing. Another patterning method based on the imprinting process
Fig. 4. (a and b) Schematic illustration of the nanotransfer printing process for (a) 2D and (b) 3D metal nanostructures. The metal nanostructures can be applied as the etching
masks for underlying substrate. (c) Tilted and (d) cross-sectional SEM images of multichannel nanostructures made by transferring textured Au film onto GaAs substrate.
Reprinted with permission from Ref. [30] (Copyright 2003 American Chemical Society).
101
is the nanotransfer printing (nTP). The nTP process was first devel-
oped in 2002 by Loo et al. [25]. This nTP technique relies on tai-
lored surface chemistries to transfer metal films from the raised
regions of a stamp to a substrate when these two elements are
brought into intimate physical contact. When the bonding strength
between the metal patterns and substrate is larger than that
between metal patterns and stamp, the metal patterns would be
transferred from the stamp to the substrate. Therefore, how to
increase (decrease) the bonding strength between the metal/sub-
strate (metal/stamp) is a critical issue. Typically, the bonding
strength between metal and stamp is decreased by introducing a
self-assembled monolayer (SAM) that ensures the weak adhesion
between the metal and stamp [26]. On the other hand, versatile
methods for improving the bonding between the metal and sub-
strate are studied. For example, the metal patterns can be trans-
ferred onto the Si substrate via the Ti-O-Si bonding [25]. Self-
assembled monolayer of 3-mercaptopropyltrimethoxysilane (MPT-
MS), alkane dithiol have been applied as the bonding layer for
transferring Au patterns [27–30]. Because the thiol group will
strongly bond to the surface of Au, these SAM would be an effective
bonding layer for nTP. The most attractive feature of the nTP
method, as well as the reversal NIL and template stripping meth-
ods that we will introduce later, is its ability to construct 3D nano-
structures that other NIL-based techniques could not do. The NIL
involving lift-off process, direct NIL, and the etching process typi-
cally lead to the formation of 2D metallic nanostructures. 3D nano-
structures were difficult to achieve in these methods. On the other
hand, Zaumseil et al. have used the nTP to transfer 3D nanostruc-
tures onto GaAs substrate (Fig. 4) [30]. By repeating the nTP, a mul-
tilayer nanostructure could be readily obtained. In the structures,
the first layer adhered to the GaAs substrate through covalent
bonds to the dithiol monolayer. Cold welding bonds the subse-
quent Au layers to each other [30].
2.4.2. Reversal NIL
Another similar process is the reversal imprint technique devel-
oped by Huang et al. in 2002 [31]. In the early stage, the reversal
imprint technique was used to transfer polymer patterns onto sub-
strates. To begin the process, a polymer layer was first coated on a
patterned mold, and then the polymer layer was transferred to a
substrate under an elevated temperature and pressure. The rever-
sal imprinting technique performs an advantage over conventional
102 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119
NIL by allowing imprinting onto substrates that cannot be easily
spin coated, such as plastic substrates. Fig. 5 displays the schematic
illustration of the three types of reversal imprinting in comparison
with the conventional NIL. In conventional NIL, the mold is pressed
into a flat polymer film at a temperature well above Tg (Fig. 5a). At
this temperature, the polymer becomes flowed and deforms easily,
and therefore it is able to copy the shape of mold. At the tempera-
tures above Tg, similar polymer flow can also be observed in rever-
sal imprinting technique. Even if the mold is textured (Fig. 5b), the
polymer on the protruded areas on the mold can be filled into
nearby cavities during imprinting. Under such conditions, the
action of reversal imprinting technique is very similar to that of
conventional NIL. On the other hand, if the reversal imprinting
technique is carried out at a temperature around or even slightly
below Tg, the behavior of the reversal imprint technique is distinct
from that of the conventional NIL and the reversal imprinting at a
temperature above Tg. At a temperature around or slightly below
Tg, the as-fabricated patterns are largely determined by the degree
of planarization of the textured mold. For example, nonplanarized
coating of polymer on the textured mold will lead to a negative
replica of the mold on the substrate, this kind of reversal imprint-
ing mode leads to a positive-replica pattern instead (Fig. 5c). On
the other hand, if a flat coating of polymer is achieved, the entire
coated polymer layer can be transferred onto the substrate
(Fig. 5d). Similar to the imprinting mode in Fig. 5b, a negative rep-
lica of the textured mold is obtained.
Reversal imprinting technique can be used to transfer metal
patterns as well. Instead of the polymer film in conventional rever-
sal imprinting, a metal film is deposited onto the textured mold in
(a)
(b)
(c)
(d)
Fig. 5. Schematic illustrations of (a) conventional NIL, (b–d) reversal NIL at temperatures (b) higher than Tg, (c) around Tg with nonplanarized coating of polymer layer, and
(d) around Tg with planarized coating of polymer layer.
the reversal imprinting for metal materials. Moreover, ultraviolet
(UV) curable resist acts as the bonding layer and is spin-coated
onto a target substrate. We have utilized the reversal imprint-in-
metal (RIM) to transfer 2D hole arrays, corrugated films and crater
arrays onto glass with an intermediate resist layer (Fig. 6) [32]. One
of attractive features of the RIM method is that metal films featur-
ing various profiles could be readily fabricated and replicated from
various molds subjected to low imprinting pressures. Metal pat-
terns could be transferred from the mold to the resist-coated sub-
strate under extremely low pressure (<0.1 MPa) because of the
surface energy difference between the surfactant and adhesion
promotion layer of the UV-cured resist. Depending on the imprint-
ing pressure and the morphology of the mold, different modes of
RIM were revealed. For example, applying a pyramid mold and a
certain pressure would lead to whole-transfer of the metal film,
resulting in a 2D corrugated metal film (Fig. 6a and b). This behav-
ior was similar to the reversal imprinting mode in Fig. 5b and d, in
which a negative replica of the mold was obtained. On the other
hand, if a hole array mold and low pressure process were applied,
only the metal film on the protruded areas of mold would contact
with the resist layer, and thus a patterned metal film with a posi-
tive replica of the mold could be obtained (Fig. 6c and d), as similar
to the mode in Fig. 5c.
Besides, complicated 3D structures can be fabricated via the
RIM process. We demonstrated a 3D crater arrays using the RIM
process (Fig. 6e and f) [32], with a reversal imprinting mode similar
to that in Fig. 5b and d. The final morphologies of the as-trans-
ferred nanostructures depended on the shapes of the molds. For
2D hole arrays, the Si mold with flat top was used. On the other
 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119 103

(a) (c) (e)

(b) (d) (f)

Fig. 6. SEM images of the (a) pyramid, (c) flat-top hole array, (e) sharp-tip hole array Si molds, and the as-transferred (b) 2D corrugated, (d) 2D hole array, (f) 3D crater array
metal film. Reprinted with permission from Ref. [32] (Copyright 2009 Optical Society of America).

hand, a sharp-tip mold, controlled by RIE etching process, was used
to transfer the 3D crater-like structures. Because the UV curable
resist could fill into the cavities of the 3D patterns on the mold,
the transferring process could be carried out much easily.
2.4.3. Template stripping
The template stripping (TS) process is another kind of pattern-
transfer technique that aims to fabricate metallic patterns with
ultra-smooth surface (Fig. 7) [33–38]. The surface roughness of
the metallic patterns was typically determined by the metal depo-
sition process, as those do in most lithographic and NIL process.
The surface roughness would greatly influence the plasmonic
properties of the as-fabricated metallic patterns, and therefore it
would be an important factor for fabricating plasmonic devices.
To prepare metallic patterns with ultra-smooth surface, the TS
method was developed accordingly. The flatness of the metallic
patterns largely depends on the surface roughness of the mold.
To begin the process, a thin metallic film was first deposited onto
the smooth template surface by thermal evaporation, sputtering
deposition or other deposition methods. Subsequently, a thermal-
or UV-curable epoxy resin was coated on top of the metallic film
surface and attached to a solid substrate. In the last, the metallic
film could be mechanically cleaved from the mold because of the
weak adhesion in between. Due to the lattice mismatch between
metal and the mold material, take Si and Au for example, the cleav-
age will occur at the Si–Au interface, leading to the Au surface fea-
turing the roughness similar to that of the mold surface. Therefore,
the TS process presents an ultra-smooth surface on the metal pat-
terns. Additionally, large areas of ultra-smooth metal surfaces can
be readily produced in a few simple steps, making the process low-
cost and high-throughput. Notably, although the procedures in the
nTP, RIM, and TS method are similar, there are some important
points in the TS method. Generally, the template stripping method
focuses more on the smoothness of the transferred metal films.

Fig. 7. Schematic illustration of the template stripping process: (a) A patterned mold with atomically flat surface was prepared. (b) Subsequent metal deposition formed a
smooth interface with the underlying mold, even though the backside of the as-deposited metal is rough. (c) thermal- or UV-curable epoxy resins was coated on top of the
metallic film surface, (d) the metallic film was mechanically cleaved from the mold because of the weak adhesion in between. Now the patterned metal film displayed a
smooth surface comparable to that of the mold. Reprinted with permission from Ref. [33] (Copyright 2011 American Chemical Society).
104 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119
Therefore, a textured mold with smooth surface is always used in
the TS method. Mica is first used as the material for mold in TS,
for it demonstrated an atomically flat surface of the cleavage plane
[37,39,40]. The problem of using mica as the mold is the delamina-
tion of its layer structure. An alternatively and much generally
used material is the polished Si wafer. With a comparable, atomi-
cally flat surface, the outstanding mechanical resistivity of Si wafer
makes it a good choice in TS. By using a textured mold with an
ultra-smooth surface to transfer the metal patterns, the metal
nanostructures will demonstrate a smooth surface comparable to
that of the mold, which will benefit the surface plasmonic
property.
Yang et al. used a similar TS process to fabricate 3D protruded
and recessed hole arrays [41]. They first deposited a metal film at
oblique angles onto a pyramidal Si template, and then applied
the UV curable polyurethane (PU) layer to strip the 3D structures
from the template, leading to 3D protruding hole arrays. On the
other hand, the recessed hole arrays were obtained by using PU
replicas. Recessed 3D hole arrays were fabricated by the angled
deposition of Au on the PU replicas. First, the pyramidal Si template
was used to shape the poly(dimethylsiloxane) (PDMS). Then the
PDMS mold was used to fabricate PU replicas. Recessed hole arrays
were generated by the further angled deposition of Au on the PU
replicas. Notably, the tapered ends of the 3D hole arrays were
extremely sharp because of the shadowing by the edges of pyrami-
dal pits during angled deposition of metal film.
Besides the crater-like or hole arrays, 3D anisotropic nanostruc-
tures can be fabricated by the RIM or TS method as well. Suh et al.
demonstrated 3D bowtie nanoantennas by the TS method [42]. A
Cr nanohole array on anisotropically etched Si(1 0 0) was used as
the template. The orientation of the bowtie dimer depended on
the direction of the angle deposition of metal film. After depositing
process, the Cr–Au film was etched away, and the 3D bowtie
antennas were left on the Si template. By applying the TS method,
(a)
Fig. 8. (a) Schematic illustration of template stripping method for the fabrication of 3D bowtie antennas. (b–d) SEM images of (b) Type A and (c) Type B dimer in etched Si
template. (d) Type A dimer embedded in PU. Inset: tilted view. Reprinted with permission from Ref. [42] (Copyright 2011 American Chemical Society).
the antennas were transferred onto transparent substrates accord-
ingly. Since the TS method was high-throughput in production,
large-area 3D Au bowties could be obtained in one step process.
Fig. 8a depicts the two types of bowties having different local cur-
vatures near the gap and the dimer direction, controlling by the
deposition conditions. Type A bowties had a folded edge parallel
to the long axis of the dimer because they were produced along
the diagonal of the pyramidal pit (Fig. 8b and d). On the other hand,
Type B bowties were formed by dimer on the two opposite Si(1 1 1)
faces of the pyramidal pit template, so the individual pattern were
flat with no folding (Fig. 8c). Noticeably, the adhesion support sur-
rounding the Au bowtie structures filled into the region around the
Au dimers as well as the gap in between.
2.5. Optical properties and applications of metal nanostructures
prepared by NIL
The metallic nanostructures display special plasmonic proper-
ties. For example, the elliptical Au nanodisks fabricated by NIL
involving lift-off process demonstrated two resonance peaks, one
in the visible and the other one in the near-infrared (NIR) regime,
due to the anisotropic feature [12]. The resonance peak in the vis-
ible regime corresponded to the plasmonic resonance in the short
axis of the elliptical nanodisks, and the one in NIR regime was the
resonance mode in the long axis of the nanodisks. The two LSPR
peaks of the elliptical nanodisks could be utilized in sensing appli-
cation. The refractometric sensing has been demonstrated on the
nanodisk arrays. The sensitivities of the two resonance modes were
experimentally determined by the slope of a linear fit on the plot of
LSPR peak wavelength in response to the bulk refractive index (RI)
using aqueous solutions containing 0–60% glycerol. Accordingly,
the sensitivities of the short-axis and long-axis modes were 167
and 327 nm/RIU, respectively. Beside the refractometric sensing,
the elliptical nanodisk arrays were able to sense biomolecules as
(b) (c)
(d)
 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119
well. The detection of prostate-specific antigen (PSA) was demon-
strated, and the peak-shift of the LSPR band could be amplified by
the enzyme-catalyzed 5-bromo-4-chloro-3-indolyl phosphate p-
toluidine/nitro blue tetrazolium (BCIP/NBT) precipitation. Also,
the limit of detection can be further enhanced down to the diag-
nostic level.
Besides, the SPR can be excited on the interface of periodical
metallic structures and dielectric, and induce an extraordinary
transmission (EOT) that overcomes the diffraction limit. The SPR
phenomena of metallic nanostructures textured by direct NIL have
been studied [20,21]. For example, the corrugated metal film dis-
played a high EOT in the visible regime. After the flat gold film
was imprinted and shaped into corrugated morphology, the trans-
mission spectrum of the corrugated gold film displayed two trans-
mission peaks at 530 and 670 nm those arose from the SPR modes
at the air/gold and substrate (resist)/gold interfaces in the asym-
metrically corrugated metal film (i.e., air/corrugated gold film/
resist), respectively. After coating a resist film as an index match-
ing layer above the corrugated gold film, the transmission of the
symmetric structure (i.e., resist/corrugated gold film/resist)
increased dramatically. This index matching effect was presumably
because of the surface plasmons excited at the two interfaces had
the same wave vector and resonated with one another. In the
index-matched structure, a strong transmission peak of 45% at
680 nm was observed, and was much higher than that of the flat
gold film. The imprinting pressure largely influenced the morphol-
ogy of the corrugated metal film and thus its plasmonic property.
The EOT of corrugated metal film increased dramatically from 3%
to 50% after increasing the imprinting pressure from 2.5 to
16 MPa. Besides, it was evident that there was no change in the
thickness of the corrugated gold films during imprinting under var-
ious imprinting pressures. Besides, as mentioned above, a sharp-tip
cone mold was used to perforate nanohole arrays into the metal
film. In the asymmetric nanohole arrays structure (air/perforated
gold film/resist), the EOT occurred at around 530 nm, which repre-
sented the SPR mode of the air/gold interface. After an index
matching layer was coated above the perforated gold film, the
SPR mode of the resist–gold at 680 nm in the symmetric structure
(resist/perforated gold film/resist) increased dramatically to 27%.
The corrugated metal film has been applied as a refractometric
and biosensor [21]. The corrugated metal film demonstrated two
sensing criteria based on the SPR wavelength-shift of Au/super-
strate mode and the intensity change of Au/substrate mode. The
refractometric sensitivity was up to 800 nm/RIU, which was com-
parable or even higher than other types of SPR-based sensors.
Moreover, the 3D nanohole arrays demonstrated unique plas-
monic properties. The comparison of anisotropic 3D nanohole
arrays to the 2D one has been made [41]. For example, the 2D
nanohole arrays may support SPR on the Au/substrate interface
and the Au/superstrate interface. As demonstrated by Yang
et al., there were five SPR bands in the 2D structure. The (1, 0)
modes from Au/substrate and Au/superstrate interfaces shifted
to longer wavelengths as incident angle (h) increased. The
(1, 1) and (0, ±1) modes from the Au/substrate interface
started to emerge at h = 20°. Besides, the (1, 0) mode from the
Au/substrate interface shifted to shorter wavelengths as h
increased. On the other hand, the anisotropic 3D nanohole arrays
displayed distinct plasmonic property from the 2D nanohole
arrays. For example, the SPR mode at the Au/superstrate interface
of the 3D protruding nanohole arrays and that at the Au/substrate
interface of the 3D recessed nanohole arrays were not observed.
Also, the 3D nanohole arrays showed regimes with high EOT.
For protruding hole arrays, regimes of high EOT emerged at high
excitation angles (h > 30°) between 600 and 800 nm whereas the
broad transmission region was centered around 530 nm for
recessed 3D hole arrays. As described above, the SPR and LSPR
105
are very sensitive to the changes in environmental dielectric con-
stants, and therefore they can be utilized as a sensing method.
The plasmonic property of the 3D recessed nanohole arrays were
further characterized by depositing polymer layers with con-
trolled thickness on top of the structures. By means of this
method, the decay lengths of SPPs and LSPs could be verified.
As expected, the SPP responded linearly to the thickness of the
polymer layers. The SPP decay length (>300 nm) was much longer
than that of the LSP, whose wavelength-shift saturated at about
11 layers (ca. 60 nm).
Moreover, the plasmonic property of the 3D bowtie arrays was
characterized by transmission spectra [42]. The zero-order trans-
mission of Type A bowties having an average d = 20 nm showed
two distinct extinction dips at 660 and 850 nm when the polariza-
tion of incident light was parallel to the dimer axis. The two extinc-
tion dips originated from the plasmonic hybridization in the
bowtie dimer as in the case of NP dimer. The short-wavelength
dip at 660 nm represented the anti-bonding mode while the
long-wavelength dip at 850 nm was the bonding mode. Notably,
the wavelength of bonding LSP mode would blue shift and become
weaker if the gap size was increased, and now the bowtie dimer
would act as two isolated particles. On the other hand, when the
polarization of incident light was perpendicular to the dimer axis,
the resonance centered at 800 nm did not change significantly for
all gap sizes. Because under this polarization, there was no cou-
pling between the NPs in the bowtie dimer, and therefore the
gap sizes did not influence the resonance wavelength. In contrast
to Type A dimers, Type B bowties did not perform two extinction
dips in the transmission spectra when the polarization of incident
light was parallel to the dimer axis. This was resulted from the
structural feature in Type B bowtie dimer could not concentrate
charges in an asymmetric fashion. Only a bonding mode resonance
at 810 nm was revealed. Moreover, when the polarization of inci-
dent light was perpendicular to the dimer axis, the resonance
wavelength did not shift, and was determined only by the particle
size, similar to Type A dimer.
Besides the photonic devices, these metal nanostructures pre-
pared by NIL have been utilized on electronics, mechanics, and
medical applications. Field effect transistors (FETs) have been
developed by NIL [17,38]. For example, Zhang et al. used NIL to pre-
pare 60-nm channel metal–oxide–semiconductor field-effect tran-
sistors (MOSFET) on whole 4-inch wafers [17]. NIL was used to
define the active areas, gates, and vias of the MOSFET at different
steps of the fabrication process. Also, multistep NIL has been pro-
posed to fabricate bottom-contact, bottom-gate thin-film transis-
tor (TFT) on Si and poly(ethylene naphthalate) (PEN) foil [43].
The NIL was performed to pattern of all layers of metal-insula-
tor-metal stacks. The gate, source-drain, and contact hole was
readily formed by NIL, with an alignment precision of 25–200 nm
on Si and 50–300 nm on foil substrates. The performance of the
as fabricated TFTs, with a channel length of 5 lm, was comparable
with the devices prepared by photolithography. Also, the TFTs with
a channel length of 250 nm on Si and 500 nm on PEN foil have been
prepared by NIL as well. Moreover, the molecular-electronic cir-
cuits and electrochemical transducer were established by NIL
[44,45]. The NIL was used to pattern the metal electrodes, with a
precise control over the electrode widths and spacings. The as-fab-
ricated transducer could be applied on the biochemical sensor,
which showed the sensitivity to the ferrocene dicarboxylic acid
[45]. Metallic scanning probe microscopy (SPM) tips have been
prepared by the NIL as well. A cone-shaped template was used to
imprint Ag-polymer mixtures in order to obtain a metallic tip. After
the imprinting process and focus ion beam milling, a high aspect
ratio, small-radius Ag tip was readily achieved. And this Ag tip
could be further applied on the SPM applications. Besides, a novel
interdigitated cantilever array structure and ultrahigh-frequency
106 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119
surface acoustic wave transducers were all demonstrated by NIL
fabrication [46,47].
3. NIL for ceramics
Ceramic is an inorganic material that generally consists of metal
oxides. Ceramic has long been used in human life, and also has
many applications in industry. The physical properties of ceramic
are well known as high hardness and mechanical resistivity. How-
ever, the brittle property makes ceramic difficult to shape by exter-
nal stress. Because NIL relies on the physical deformation of the
target materials suffering the imprinting by mold, a brittle material
seems an inferior choice in NIL process. To overcome this issue,
many NIL-based methods have been developed.
3.1. NIL involving dry etching process
To avoid the stress-induced failure on the ceramic materials
during imprinting process, dry etching process is generally used
to fabricate patterns on ceramic materials. The etching masks are
typically made of metal patterns defined by NIL [48,49]. For exam-
ple, nano-scaled patterns on epitaxial Ba0.7Sr0.3TiO3 (BST) ceramic
films were fabricated by NIL. As demonstrated by Jim et al. [48],
the BST film was first deposited on substrate by pulsed laser depo-
sition. Then PMMA and imprint resist were spun on the BST film
subsequently. The patterns were transferred onto the imprint
resist and PMMA. A Cr thin film was then deposited onto the pat-
terned resist, and the following lift-off process led to the patterned
Cr. The Cr acted as the etching mask for the underlying BST film.
After carrying out the ICP (inductively coupled plasma) etching
and Cr removal, the 2D BST nanostructures were obtained. The
BST nanostructures with different periods, and Si replicas could
be fabricated from a single master mold.
The same procedure can be applied on other ceramic films like
sapphire. Sapphire is a robust substrate that finds many applica-
tions in optoelectronic device. For example, sapphire is widely
used as the substrate of a GaN-based light emitting diode (LED)
[50–52]. Recently, several studies have examined the application
of patterned sapphire substrate [53,54]. While the device perfor-
mance is enhanced significantly by the patterned sapphire, the pat-
tern shapes are still random. NIL can be applied to fabricate
sapphire substrates with designed textures [55–57]. For example,
with the same procedure in the conventional NIL, the patterns
were first transferred by pressing a flexible polyvinylchloride
(PVC) stamp into the UV curable resist along with UV light expo-
sure [55]. Then the patterns were further transferred to the under-
lying resist layer with O2 plasma etching. Lift-off process of Cr
(g)
(i)
Fig. 9. (a–f) Schematic illustration of the NIL-based Mo lift-off method. (g–j) SEM images of FMO nanodots having a size of (g) 1 lm, (h) 500 nm, (i) 200 nm, and (j) 120 nm.
Reprinted with permission from Ref. [59] (Copyright 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).
formed the etching masks on top of the sapphire substrate, and
the sapphire substrate was textured by ICP etching. Finally, the
periodical patterns were successfully transferred onto the robust
sapphire substrate.
3.2. NIL involving lift-off process
For metal materials, lift-off is a common process for fabricating
metallic nanostructures. The similar method can also be adopted
on ceramic materials. By means of the lift-off process, ceramic
nanostructures could be readily obtained. For example, Suresh
et al. fabricated robust, high-density ZnO nanopillar arrays using
NIL involving lift-off process [58]. Briefly, a Si pillar mold was pre-
pared by block copolymer lithography. Then the mold was
imposed into PMMA resist layer followed by a plasma etching to
remove the residual resist at the bottom of the holes. ZnO film
was deposited onto the textured resist layer by selected area
atomic layer deposition (ALD). Followed by the lift-off process,
ZnO nanopillar arrays were obtained. These patterns presented a
uniform array of ZnO nanopillars with sub-100 nm features and
spatial resolutions. Moreover, these nanopillar arrays exhibited
narrow distributions in size and separation, and good mechanical
stability.
This strategy is general and extendible to other materials that
can be grown through not only ALD but also other deposition
methods. Suzuki et al. presented a method for fabricating a
large-area dot array of Fe2.5Mn0.5O4 (FMO) by a combination of
pulse laser deposition (PLD), NIL, and the Mo lift-off technique
[59]. In the procedure (Fig. 9a–f), the resist layer was patterned
by NIL, then following deposition of Mo and lift-off process left pat-
terned Mo films on the substrate. The patterned Mo films were
used as the resist for the second lift-off process instead of polymer
based resists. FMO film was deposited on the Mo resist at 340 °C by
PLD. At this high temperature, polymer-based resists would be
destroyed, and therefore the use of patterned Mo films as the resist
layer was necessary. Thus, if large-area patterned Mo films could
be obtained, large-area oxide patterns deposited in dry conditions
would be realized. After the removal of patterned Mo films, FMO
dot arrays were obtained. A FMO dot array was successfully fabri-
cated over a large area. Besides, by means of this method, the FMO
dot arrays with dot sizes ranging from 120 nm to 3 mm with very
few vacancies were readily obtained (Fig. 9g–j).
3.3. NIL involving sol–gel process
In the conventional NIL, resists (polymer) are generally used as
the materials to be imprinted. However, the imprinted resist layer
(h)
10µm 2µm
(j)
2µm 2µm
 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119
demonstrates limited thermal and mechanical stability. Therefore,
the imprinted resist layer is often used as a mask to transfer the
patterns either by etching or lift-off into a stable substrate. Besides,
the imprinting process is based on the plastic deformations of tar-
get materials, therefore it would require high imprinting pressure
if we attempt to imprint materials with high yield strength. How-
ever, ceramic materials fracture easily when imposed stress. There-
fore, the NIL on ceramics is typically carried out along with an ICP
plasma etching to transfer the patterns onto the target ceramics,
and the direct NIL on ceramics is generally limited. To facilitate
the direct NIL on ceramics, the sol–gel process was developed
accordingly. The sol–gel process is a method for producing solid
films from precursors. Sol–gel processing is widely used in the for-
mation of ceramic and glass films due to the following reasons. The
process is mainly a simple reaction that does not require exotic
materials, catalysts, or vacuum deposition process. Typically, the
hydrolysis and condensation reactions take place at room temper-
ature. Further a moderate temperature is applied to cure the gel,
removing the water or ethanol generated during the reactions.
Because sol–gel precursors demonstrate a much higher viscosity
and toughness, they can bear the stress during imprinting process,
and form patterns without failure. By using the ceramic sol–gel,
direct NIL on ceramic films is possible. We have demonstrated a
low-pressure, low-temperature direct NIL method for patterning
ferroelectric PZT [Pb(ZrxTi1x)O3] films [60,61] (Fig. 10). In general,
direct NIL in a ferroelectric or metal film utilizes ultrahigh pressure
or temperature to form patterns on the film. We improved the con-
ventional direct NIL processes by using a sharp-tip mold and an
underlying soft gel film (Fig. 10a). The sharp-tip mold will concen-
trate stress at the tips, and therefore the imprinting pressure and
temperature can be reduced. Besides, imprinting on the gel film
instead of on the bulk film makes the NIL much easily to be carried
out. After the patterns are created on the PZT-gel, a further anneal-
ing process is required to obtain the patterned PZT film (Fig. 10b
and c). Besides, it was also successfully demonstrated that the
NIL on the metal/ferroelectric bilayer structure (Fig. 10d and e)
would help to overcome the pattern flattened problem in a gel film.
Moreover, the metal film prevents the mold from directly contact
with the PZT gel. Therefore, no residual or contaminant will be
observed on the mold. Further, the metal layer can also be the
upper conductive layer in the ferroelectric application.
The sol–gel process is widely adopted in NIL for ceramic mate-
rials. Versatile sol–gel ceramic materials can be imprinted directly.
A polymeric mold is more generally used in the NIL for sol–gel
(a)
(b)
(c)
Fig. 10. (a) Schematic illustration of direct NIL for PZT and Au/PZT bilayer structures. (b–e) SEM images of (b and c) PZT and (d and e) Au/PZT bilayer structures fabricated at a
pressure of 20 MPa. (b and d) Top view; (c and e) tilted view. Reprinted with permission from Ref. [60] (Copyright 2006 American Vacuum Society).
107
ceramic films. Because the solvent in the ceramic-sol would diffuse
into and be absorbed by the polymeric mold, the ceramic-sol will
convert into the ceramic-gel. The patterned ceramic-gel is not as
viscous as the ceramic-sol, and thus it can maintain the deforma-
tion caused by imprinting. ZnO [62,63] and silica [64] patterns
were fabricated by means of the sol–gel NIL process. For example,
Yang et al. prepared ZnO patterns on Si substrates [62]. In their
study, a PDMS-based mold and ZnO-sol were used. During the
imprinting process, the organic solvent in the ZnO-sol was
absorbed by the PDMS-based mold and the ZnO-sol was thus con-
verted into ZnO-gel. These patterned ZnO-gel were subsequently
annealed to form ZnO patterns. Using this ZnO-sol imprinting
method, the feature size of ZnO nano-patterns, as small as
50 nm, were fabricated on Si and oxidized Si wafer substrates.
On the other hand, a direct indium tin oxide (ITO) patterning
technique using thermal imprint lithography was presented
[65,66]. In order to fabricate the patterns on ITO films using NIL,
the target materials (here ITO) must have sufficient fluidity to fill
into the mold and copy its morphology. Therefore, to imprint on
ITO, the ITO NP solution was used as the imprinting resist. As dem-
onstrated by Yang et al. [65], the ITO NP solution was first diluted
with N0 ,N-dimethylformamide (DMF) to reduce the viscosity and
leave sufficient residual solvent in the layer after the spin-coating
process. A PDMS mold was used to imprint on the ITO NP layer. The
solvent was absorbed by the polymeric mold, and the ITO NP was
condensed. A post annealing sintered the ITO NPs and formed the
solid ITO structures. The patterned ITO NP layer was directly fabri-
cated onto the substrate by NIL. A tapered sidewall of ITO struc-
tures was observed. This was due to the absorption of the DMF
in the ITO NP solution by the PDMS mold. The diameter and height
of the ITO structures were ca. 280 and 130 nm, respectively. The
ITO NPs were sintered together during the post annealing process
and did not affect the dimensions of the ITO patterns.
3.4. Reversal NIL
Beside the direct NIL on sol–gel ceramic films, the reversal NIL
has been used to pattern ceramic films. Similar to the reversal
NIL for metals, the reversal NIL also demonstrated the ability for
constructing 3D ceramic structures, which was hard to achieve in
the NIL involving dry etching. In the process [67], the template sur-
face was first modified using (1H, 1H, 2H, 2H-perfluorooctyl)tri-
chlorosilane to form an anti-stick layer so that the PZT gel could
be easily separated from the template. Then the PZT gel was spun
(d)
(e)
108 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119

onto the template to copy the morphology of the template. The
template with PZT was then pressed onto a substrate at room tem-
perature. After that, the substrate was directly separated from the
template. As PZT on top of the grating lines contacted the sub-
strate, it was peeled from template while PZT in trenches stayed
in the template.
The reversal NIL can be applied on manufacturing multilayer
ceramic structures as well. Han et al. demonstrated 3D ZnO struc-
tures by reversal NIL (Fig. 11a) [68]. A high-refractive-index ZnO
NP-based resin was used as the imprint resin in their study. The
ZnO NP-based resin was formed by dispersing 10% of ZnO NPs hav-
ing a diameter of 40 nm into a 1:5 mixture of benzylmethacrylate
(BMA) monomer resin and ethanol. To begin the reversal NIL, the
ZnO NP-based resin was spin-coated onto a polyvinyl alcohol
(PVA) transfer template and covered with an imprinting mold
made by polymeric PDMS. The PDMS mold would absorb the sol-
vent from the imprint resin. Besides, the PDMS mold would pro-
vide a better conformal contact with the substrate. Therefore, a
PDMS mold was superior to other polymeric molds for patterning
the solution-based resin. The PVA transfer template and the PDMS
mold, sandwiched with the imprinted resin, were pressed toward
each other under vacuum with UV exposure to completely cure
the resin. Then the patterned ZnO nanostructures were transferred
by pressing the ZnO structures attached to the PVA transfer tem-
plate onto the target substrates. The PVA transfer template was
then washed away by deionized water, leaving the ZnO structures
on the substrate. By repeating the same transfer procedure, 3D
multilayer ZnO structures could be obtained. Fig. 11b and c display
the SEM images and schematic structures of the 3D ZnO nanostruc-
tures transferred onto a Si substrate. The cross-sectional SEM
image and schematic structure of one-layer patterned ZnO nano-
structure on a Si wafer are shown in Fig. 11b. Also, the two-layer
structure is displayed in Fig. 11c. UV-curable resist layer was used
to glue the ZnO layers. As shown in Fig. 11, the UV-curable resist
did not fill into the cavities between the patterns and layers, and
the ZnO nanostructures were not damaged by the multiple cycles
of reversal NIL process. The images also demonstrate that the 3D
multilayer ZnO nanostructures can be readily fabricated using
reversal NIL with a ZnO NP-based resin, polymeric mold, and a
transfer template.
3.5. Applications of ceramic nanostructures prepared by NIL
The patterned sapphire can enhance the luminescence effi-
ciency of LEDs [55,56]. For example, a GaN based LED on a nano-
meter-scaled patterned sapphire substrate exhibited a stronger
and sharper photoluminescence (PL) emission peak than that of
the unpatterned LED [55]. Since the total internal reflection (TIR)
effect could be reduced by the nanometer-scaled structures,
stronger PL emission could be obtained. The PL peak of the LED

Fig. 11. (a) Schematic illustration of preparing 3D structures by reversal NIL. (b and c) SEM images and schematic structures of a (b) single-layer and (c) two-layer 3D
structure made by reversal NIL of ZnO NP-based resin. Reprinted with permission from Ref. [68] (Copyright 2013 IOP Publishing).
 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119
on patterned sapphire is approximately two times stronger than
that from the LED grown on the flat sapphire substrate. Further-
more, the crystalline quality of the expitaxial GaN was slightly
improved by the patterned sapphire substrate. On the other hand,
the GaN LED on patterned sapphire substrate demonstrated a elec-
troluminescence (EL) peak intensity larger than that of the LED on
flat substrate by 2.8 times, indicating the light extraction efficiency
could be improved by patterned sapphire substrates.
Besides, the patterned ZnO NP layer could be applied on LEDs as
well [68]. If the patterned ZnO layer was fabricated on the ITO elec-
trode of the LED device, it could cause a photon scattering effect
and enhance the light extraction efficiency of the LED device.
Moreover, the enhancement of light extraction efficiency of the
LED with dual-side ZnO patterns was confirmed by electrolumines-
cence (EL) intensity. The EL emission intensity of the LED with pat-
terned layer showed an increase of 11.7% compared to the flat one.
Besides, the patterned ZnO layer did not influence the electrical
property of the LED device. Therefore, the patterned ZnO layer fab-
ricated by reversal NIL showed a useful application on LED devices.
Moreover, the ZnO patterns could be incorporated within a
metal-oxide-semiconductor (MOS) capacitor. For example, as dem-
onstrated by Suresh [59], the MOS capacitor incorporating ZnO
arrays demonstrated a hysteresis of 2.82 V, which was much supe-
rior to the low hysteresis of ca. 0.4 V for the control substrates
without ZnO structures. The results showed the good charge stor-
age in the MOS capacitor with ZnO arrays. Besides, capaci-
tancetime measurement indicated that the excellent charge
retention ability in the capacitor, which was resulted from the
well-patterned and spatially isolated ZnO patterns that reduced
leakage through lateral conduction as well as reduced stress
induced leakage.
On the other hand, ITO is widely used as a transparent conduc-
tive electrode. A patterned ITO film could further improve the
transmission of incoming light [65]. The transmittances of ITO
glass and directly patterned ITO film were compared. The directly
patterned ITO film demonstrated a higher transmittance than that
of the flat ITO glass due to the antireflection effect by the ITO pat-
terns. Moreover, after the annealing process, the sheet resistance of
the ITO NP patterns on the ITO glass was similar to that of the flat
ITO glass. Overall, the transmittance of ITO glass could be enhanced
while maintaining its conductivity using ITO NP patterns on the
ITO glass. Therefore, it could be applied as a high efficiency trans-
parent conductive electrode for light emitting diodes, flat panel
displays, and photovoltaic devices.
4. NIL for flexible plastic materials
Plastics are polymer materials based on chains of carbon and
other side groups or atoms. Depending on the polymer chains,
molecular mass, degree of crystallinity, and many other factors,
the material properties of plastics are diverse. Generally, plastics
are flexible and moldable, especially at an elevated temperature.
Plastic substrates are typically transparent in visible regime, and
therefore are widely adopted as supports for flexible devices.
Besides, due to the low cost and flexibility, plastics are suitable
for large-area patterning by NIL.
4.1. Direct NIL
Compared to metals and ceramics, plastic materials are highly
deformable, and therefore the most efficient way to pattern plastic
materials is the direct NIL. Schift et al. have fabricated a dense two-
dimensional periodic photonic bandgap structures in PMMA thin
films using NIL [69]. A stamp with a high-aspect-ratio pillar array
was used as the imprinting mold to fabricate nanostructures on
109
PMMA film. The stamp was obtained via a two-step copying of
the original mold made by electron beam lithography. Then the
PMMA were spin-coated on glass as the imprinting resin. To fabri-
cate the high-aspect-ratio nanostructures, the demolding process
was a critical step. For a failure in the demolding process, the as-
fabricated structures might be crushed. For example, the friction
force generated at the polymer/stamp interface would lead to dif-
ficulties in demolding. The friction force might be enhanced by the
shrinkage and thermal expansion differences between the two
materials. The local friction force resulted in a non-uniform
demolding, as well as the as-fabricated structures. Dense gratings
with high aspect ratio structures would exert high demolding
forces on the structures, leading to some distortions or abrasions
on the structures. Besides, local ripping of the substrate surface
might be presented. On the other hand, the difference between
the molding and demolding temperatures would largely influence
the final structures as well. In this case, the damage might be
avoided by demolding at temperatures only slightly below the Tg
of the PMMA. This aimed to reduce the mismatch of thermal
expansion between the PMMA and the stamps. Besides, at this
temperature, the PMMA might still be soft enough to be released
from the stamp. The high-aspect-ratio, two-dimensional photonic
bandgap structure could be obtained accordingly.
Wafer-scale direct NIL using on plastic substrate has been dem-
onstrated as well. Similar to the NIL on resist layer, the direct NIL
on plastic substrates was performed at an elevated temperature
around Tg of the plastic substrate [70]. Polycarbonate (PC) is com-
monly used as a high-transmittance polymer-based substrate, and
it is considered as a promising candidate for fabricating optical
components or devices. In our previous study, Si master molds fab-
ricated by electron beam lithography were employed. A dual-side
direct NIL on a 365-lm-thick PC substrate was demonstrated. First,
the PC substrate was placed between two Si master molds having a
line width of 180 nm and a period of 400 nm. For the ease of
imprinting, the PC substrate was softened through a preheating
treatment. Because the PC substrate possessed a Tg of ca. 150 °C,
the system, including the PC substrate and the Si master molds,
was preheated at a slightly higher temperature of 170 °C. Next,
an imprinting pressure of 15 MPa was applied for the imprinting
process for 3 min. After releasing the pressure, the system was rap-
idly cooled by immersion into ice water, and then the textured PC
substrate was demolded from the two master molds.
The procedure of dual-side nanoimprint on PC substrate takes
advantages of physical properties of PC. First, like other polymer
materials, the PC substrate performs phase transformations at a
specific temperature. Therefore, the PC substrate will transform
from rigid state to rubber-like state and become much softer at
the Tg. As in the conventional NIL for resist, this phenomenon aids
the nanoimprint process because the softened underlying sub-
strate will largely reduce the applied pressure. Besides, the rub-
ber-like PC substrate is much easily deformed when suffering
external pressure compared to the rigid counterpart. On the other
hand, under the consideration of demolding, a substrate that will
not stick to the molds is much preferred. The polymer will flow
and stick to the molds if the cooling rate is too slow during
demolding. Therefore, rapid cooling of the PC substrate after
imprinting is necessary to maintain the shape of textured PC sub-
strate and ease the demolding process. Fig. 12 displays photo-
graphic images of an as-fabricated textured PC substrate. A clear
diffraction pattern was evident on the PC substrate, revealing that
large-area grating structures were successfully fabricated on the PC
substrate. Moreover, a deliberately mismatch in the upper and bot-
tom master molds during the imprinting process allowed a clear
observation of the diffraction pattern from the rear side when
observing from the front side, as in Fig. 12a (white arrow)—direct
evidence that grating structures were readily fabricated on both
110 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119
Fig. 12. Photographic images displaying (a) the diffraction pattern of a textured PC sheet and (b) a bent textured PC sheet. (c) AFM images of textured PC sheet. Reprinted
with permission from Ref. [70] (Copyright 2011 The Electrochemical Society).
sides of a PC substrate. Fig. 12b demonstrates the flexibility of the
textured PC substrate, which was easily bent; the diffraction pat-
tern was clearly evident. Such flexibility might lead these textured
plastic films to have a much wider applicability, relative to typical
rigid ones, in flexible optoelectronic devices or systems. Fig. 12c
presents atomic force microscopy (AFM) images of the dual-side
textures on a PC substrate. The top-view image demonstrates the
existence of a uniform periodical grating structure over a large
area. The inset reveals the 3D morphology of the grating structure.
The depths of the trenches of the textured PC substrate were ca.
340 nm. The total trench depth was ca. 600 nm, as expected for
the sum of those of the two sides. Notably, the trench depth at each
side was around 300 nm, which was shallower than that of the Si
master mold (depth = 600 nm). The trench depth of the textured
PC substrate was highly dependent on the applied pressure during
imprinting process and the viscosity of imprinted substrate. The
trench depth of the textured PC substrate would increase with
the applied pressure. However, due to the moderate viscosity of
PC substrate, unlike other fluidic materials such as PDMS and
SU8, it was difficult to replicate exactly the same the trench depth
of Si master mold for PC substrate.
Besides, high-aspect-ratio sub-wavelength structures (SWSs)
have been fabricated on PMMA plate as well, as demonstrated by
Ting and co-workers [71]. They applied an electron cyclotron reso-
nance (ECR) plasma etching process using gas mixtures of silane,
methane, argon and hydrogen to directly fabricate the tapered
nanotips on Si substrates in large area. Then a Ni–Co metal mold
was produced through the replication of the Si nanotips by electro-
plating. The as-fabricated Ni–Co metal mold was used to imprint a
PMMA sheet. The hot-embossing process was performed at various
temperatures. At a low temperature of 110 °C, for example, the
PMMA had a less deformation because the temperature was just
close to the Tg of PMMA (100–110 °C). The PMMA flowed into
the cavities of the Ni–Co metal mold with great difficulty at this
low temperature. Moreover, the low mobility of PMMA resulted
in the incomplete filling of the PMMA into the cavities, leading to
nanostructures with a low aspect ratio of about 1.2–1.6. On the
other hand, if the molding temperature increased to 135 °C, the
PMMA flowed easily into the cavities of the mold, and thus the
aspect ratios of as-fabricated structures increased to 2.6–3.0, which
was much larger than that obtain at 110 °C. Moreover, when the
temperature increased to 160 °C, the aspect ratios of the PMMA
nanostructures could achieve up to 4–5.3. The heights of the
PMMA nanostructures were ca. 480–600 nm, and performed very
sharp tips. There was almost no distortion in the diameter of
PMMA nanostructures compared to that of the Si and Ni–Co mold.
The diameter of the nanostructures were almost the same in the
above three cases. The depth of the nano-cavities in the Ni–Co
mold was only about half the height of the nanotips in the Si mold.
On the other hand, the heights of the PMMA nanostructures were
nearly identical to the depth of the Ni–Co mold when the PMMA
sheet was imprinted at a high temperature of 160 °C.
4.2. Reversal NIL
Besides the direct NIL for plastic or polymer materials, the
reversal NIL is applicable for these highly deformable materials
as well. The advantage of using reversal NIL to prepare the plas-
tic/polymer nanostructures is the 3D construction ability. As
described in Section 2.4, the reversal NIL of polymer was first pro-
posed by Huang et al. [31]. Versatile polymer structures could be
readily prepared by the reversal NIL. Besides the 2D planer struc-
tures, 3D multilayer structures of polymer materials could be
established by the reversal NIL as well. For example, N. Kehagias
et al. have demonstrated two kinds of reversal UV NIL methods
for constructing 3D multilayer structures. [72–74]. The schematic
illustrations of the two reversal UV NIL methods are presented in
Fig. 13. In the reversal UV NIL (Fig. 13a), the process was carried
out by first spin coating UV-curable polymer on to a patterned
mold with surface relief. The polymer-coated mold was then
brought into contact with the target substrate, and the polymer
layer was further transferred onto the target substrate under heat
and pressure. Depending on the imprinting pressure and heating
temperature, either whole layer transfer or inking layer would be
obtained. The UV exposure was carried out after the imprinting
step, which induced the crosslink of the polymer. By repeating
the same process onto the former layer, 3D multilayer structures
could be built up conveniently. On the other hand, in the reversal
 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119 111

Fig. 13. Schematic illustrations of (a) reversal UV NIL, and (b) reversal contact NIL. In the reversal UV NIL, a master stamp with surface relief was used to pattern polymer
layer. On the other hand, a transparent master stamp with metallic patterns was used to define the UV exposure areas on the polymer layer. By repeating the NIL process,
multilayer polymer structures could be readily constructed onto the previous layer in these two methods.

contact UV NIL method (Fig. 13b), the imprinting step and UV-
exposure were performed simultaneously. The master mold in
the reversal contact UV NIL method was made from a transparent
substrate with metallic patterns on top. The metallic patterns
aimed to define areas without UV exposure. Therefore, unlike the
reversal UV NIL that constructed polymer structures by the surface
relief of the master mold, the reversal contact UV NIL constructed
polymer structures by deliberately defining areas with and without
UV exposures. After the simultaneous imprinting and UV exposure,
the polymer layer was transferred onto the target substrate. With a
further development process, the polymer structures with
designed patterns were obtained. Additionally, the multilayer
structures could be achieved by repeating the process as well.
Therefore, the reversal NIL method not only provided an efficient
way to establish various kinds of 2D polymer structures but also
demonstrated its ability to construct 3D structures with
functionalities.
4.3. Roll-to-roll NIL
Plastic film possesses outstanding flexibility and deformability,
and they are widely used as underlying support in versatile flex-
ible optoelectronic devices. Besides, patterned plastic films pro-
vide additional functionalities to the planar one. One great
advantage of plastic film is the compatibility with the roll-to-roll
(R2R) process. Therefore, the patterning of plastic film can be
achieved in low cost and high throughput via the R2R NIL pro-
cess. Many studies have been devoted to develop a rapid R2R
NIL process [75–86]. A general schematic illustration of R2R NIL
process is shown in Fig. 14 [75]. The patterning mechanism in
the R2R NIL procedure is similar to the conventional imprinting
or embossing process, but the speed is much higher, at least
one or two orders of magnitude larger than that of the conven-
tional NIL. Therefore, large-area patterned plastic film could be
obtained in a relatively short time. Notably, although the R2R
NIL produces patterns by imprinting or embossing, there is a
main difference between the R2R NIL and conventional NIL. The
first difference is area of contact region. In the conventional
wafer-scale NIL, the contact area between mold and the
imprinted target materials such as polymer or resist is very large
whereas the contact area in R2R NIL is a narrow region transverse
to the web moving direction. It is known that the adhesion force
is proportional to the interface areas, and the large contact area in
conventional NIL would lead to a considerable adhesion force
between the mold and the imprinted target material. A large
adhesion force would make the demolding process difficult to
carry out. On the other hand, the contact region is relatively small
in the R2R NIL process; therefore the demolding process should
be easily performed due to the low adhesion force. Moreover,
because the R2R NIL applies a roller mold, the demolding process
will proceed in a ‘‘peeling’’ fashion, leading to a much lower force
required for separation [75].
112 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119

Fig. 14. (a) Schematic illustration of the R2RNIL process on plastics. The subsequent metal deposition process is optional and dependent on the final applications. (b) The
coating unit and (c) the imprint unit of the R2RNIL apparatus. Reprinted with permission from Ref. [75] (Copyright 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).

For plastic films, a direct R2R NIL is desirable. This can be
achieved by performing the R2R NIL process at elevated tempera-
tures. For example, Lim et al. demonstrated a roller NIL (RNIL) sys-
tem for patterning plastic films by employing a hard mold [76]. In
this system, a hard Si or quartz stamp was placed on a hot plate in
order to heat the plastic film to be imprinted. A roller rolling on the
stamp pressed the flexible plastic film into contact with the hard
stamp line by line. Guide rollers following the press roller aimed
to prevent the plastic film from shrinking or stretching during
the RNIL process. The resolution of the transfer patterns depended
on that of the hard stamp. For the demonstration in this study, the
line width and pitch of the line pattern on the stamp were 180 nm
and 470 nm, respectively. A roller of PC film with a thickness of
0.38 mm and a width of 150 mm was installed as a flexible sub-
strate. The temperature of the system was heated to 165 °C (above
the Tg of PC) and was cooled by a jet of compressed air. Notably, a
higher imprinting temperature would lead to thermal deformation
of the PC film whereas a lower imprinting temperature would
result in an incomplete deformation as well as the pattern transfer.
In the same manner, higher imprinting speed would lead to incom-
plete pattern transfer, and lower imprint speed would lead to a
complete replica of the mold but a low throughput. Therefore,
the imprinting conditions should be optimized in order to obtain
a good pattern transfer while maintain a high throughput.
Another way to build nanostructures on a plastic film is to
transfer patterned UV curable resist onto the plastic film [77].
Under this consideration, a UV light exposure was equipped with
the R2R NIL system. For example, a RNIL system adopted a soft
roller and focused UV light was developed. The soft roller aimed
to precisely control the contact pressure between the plastic film
and the stamp. Additionally, a focused UV light was used to cure
the resist coated on plastic film instantaneously. By means of this
configuration, structures of UV-curable resist could be transferred
onto the plastic film.
Not only flat plastic films but also plastic fibers could be
imprinted. Mekaru et al. demonstrated a new-type roller NIL sys-
tem to transfer designed patterns from a plane mold onto the
curved surface of a plastic fiber at high throughput (Fig. 15a)
[78]. In this system, a plastic fiber was placed between two plane
molds and rolls under the traction force of the two sliding plane
molds traveling in opposite directions. By this new-type roller
NIL system, 5-lm-width square and 5-lm-diameter circular dot-
ted patterns with 10-lm pitch were successfully transferred onto
a 250-lm-diameter plastic optical fiber (POF). Moreover, Mekaru
et al. also presented a continuous molding on the entire curved
surface of 1.6 m-long POF by a repetition of roller-imprinting for
100 times. No significant differences between the shapes and
depths of the imprinted patterns obtained from the first imprinting
 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119
Fig. 15. (a) R2R process on plastic optical fibers. (b) Optical micrographs of mold patterns and imprinted patterns on the surface of plastic optical fibers after the 1st and
100th shots. Reprinted with permission from Ref. [78] (Copyright 2010 Elsevier B.V.).
and that obtained from the 100th imprinting were observed,
implying the roller-imprinting was a reliable method for fabricat-
ing patterns onto the curved surface of a plastic fiber (Fig. 15b).
4.4. Optical properties and applications of plastic nanostructures
prepared by NIL
The structured plastic materials can be applied as an optical
component due to their intrinsic transparency. For example, the
sub-wavelength periodical gratings (SPGs) prepared by direct NIL
exhibited the birefringence [70]. The SPG structure resulted in dif-
ferent degrees of phase retardation of the TE and TM modes of
light. Therefore, artificial wave plates based on SPG structures
would have an optical fast axis perpendicular to the grating line
and a slow axis parallel to the grating line. This form birefringence
made SPG-based wave plates promising candidates for use in
phase retardation systems. The SPG structures were fabricated by
direct NIL on PC substrate as describe above, and the correspond-
ing phase retardations were measured. The dual-side SPG structure
having a depth of ca. 600 nm demonstrated a phase retardation of
0.25p, which was identical to a 1/8-wave plates. Moreover, the
degree of phase retardation could be summed by stacking the
SPG-based wave plates in series. When two SPG-based 1/8-wave
plates were stacked together, they provided a total phase retarda-
tion of 0.5p. The result suggested that any degree of phase retarda-
tion could be built into the system using such a stacking approach.
113
Therefore, changing the imprint pressure and, thus, the depth of
the SPGs, readily allowed the phase retardation to be varied for a
certain working wavelength. The low-cost and simple fabrication
of the flexible wave plates by direct NIL on plastic substrate, in
conjunction with the stacking of various SPG-based wave plates
of designed depths, allowed one to readily obtain a versatile phase
retardation systems for operation under a diverse set of selected
wavelengths.
Besides, the plastic nanostructures could be used as the antire-
flection structures [71,87,88]. For example, the reflection of the
underlying substrate could be largely reduced in the wavelengths
between 400 and 800 nm when incorporated with the PMMA
nanostructures [71,87]. Due to the gradient of refractive index,
the PMMA nanostructures with high aspect ratio and the shapes
of tapered angles reduced the reflectance dramatically. On the
other hand, this kind of tapered structures also provided an omni-
directional antireflection. A low reflectance of the PMMA nano-
structures was obtained at incident angles from 5° to 40°.
Therefore, the nanostructures can be applied on various photovol-
taic devices. Moreover, the nanoimprinted structures could help
the light harvesting in photovoltaics. By patterning the hole trans-
porting layer in an organic photovoltaic [89] or the active layer [90]
in a hybrid photovoltaic, these nanoimprinted structures showed a
great contribution to enhance the device efficiency. The increment
of the device efficiency might originate from the superior light
scattering performance from the nanoimprinted structures or the
114 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119
larger junction area in these nanoimprinted photovoltaics. Overall,
the NIL is proven as an efficiency method for constructing versatile
plastic optical components and polymer-based photovoltaics with
outstanding performance.
5. NIL for nanomaterials
From the statements above, NIL has been used to prepare versa-
tile micro- and nano-structures on metal, ceramic and polymer
materials. Nanomaterials are materials possessing dimensions in
the nanoscale, and they demonstrate distinct properties from their
bulk counterparts. The distinct properties are resulted from their
nanoscale features, and thus many unique properties have been
discovered. Therefore, nanomaterials are a new field in materials
science. Here, we will describe the NIL for three kinds of potential
nanomaterials—carbon nanotubes (CNTs), graphene, and metallic
nanoparticles.
5.1. Carbon nanotubes
CNTs are hollow cylindrical nanostructures consist of carbon
atoms on the surface. Depending on the arrangement of carbon
atoms, armchair, zigzag, and chiral types of CNTs have been grown
as well as single-wall CNTs (SWCNTs) and multi-wall CNTs
(MWCNTs) [91,92]. The outstanding physical properties such as
thermal and electrical conductivity make CNTs a superior material
in many devices [93–95]. To broaden the applications, selective
growth at certain sites of CNT arrays are desired. To pattern CNT
arrays, various lithographic methods are adopted. Moreover, as
Fig. 16. (a) Schematic illustration of fabricating CNT arrays by NIL. (b–d) SEM images of CNT arrays patterned in (b) ‘‘NANO IMPRINT’’ letters, (c) square arrays, and (c) the
enlarged area of the square arrays. Reprinted with permission from Ref. [96] (Copyright 2006 American Institute of Physics).
the NIL is depicted as an efficient method for replacing the electron
beam lithography and photolithography, it can be used to pattern
CNT arrays as well. NIL is carried out to define the growing area of
CNTs. For example, Vieira et al. demonstrated a multiwall CNT
arrays by NIL [96]. The procedure was similar to the NIL for other
functional materials. A simplified schematic illustration of the pro-
cess is depicted in Fig. 16a. Briefly, a hard master with predefined
patterns pressed into PMMA resist at a temperature above Tg. After
the demolding process, RIE was used to remove the remaining res-
idue in the patterned areas. The imprint process was performed
under vacuum to avoid the formation of air bubbles in the resist.
After the patterns were successfully transferred onto the resist,
the growing areas for CNTs were defined accordingly (areas with-
out resist). For the CNT growth, a 15 nm-thick ITO diffusion barrier
and a 7 nm-thick Ni catalyst were sputtered onto the substrate
with resist patterned by NIL. After the lift-off process, positive-rep-
lica patterned catalyst dot islands were formed on the substrate.
The growth of aligned MWCNTs was performed by plasma-
enhanced chemical vapor deposition (PECVD) using acetylene
(C2H5) and ammonia (NH3) at 725 °C. Moreover, the morphology
of the CNTs could be modified by the applied bias during the grow-
ing process. For example, by increasing the bias slightly from the
usual 600–630 V, the CNTs with a smaller tip apex were prepared
due to the Ni catalyst being etched away by high-energy ions in the
plasma as the CNT grows. Therefore, NIL has been proved as a
robust method for patterning CNT arrays. Fig. 16b–d display the
as-grown CNT arrays arranged in design patterns. It was obvious
that the CNTs only grew in the area defined by the NIL. The similar
procedure can be used to fabricate wafer-scale CNT arrays as well.
 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119 115

A 2-inch vertically aligned CNT arrays have been achieved, as pro-
posed by Bu et al. [97].
Besides, Yin et al. demonstrated two imprinting processes, soft
UV curing NIL with distortion reduction by pre-cure press releasing
(DRPPR) process (Fig. 17a) and NIL without cured residual resist
(Fig. 17b), for patterning insulated resist [98]. CNT arrays were
grown in the opening space between two insulated resist patterns
on the conductive substrate by pyrolysis of iron phthalocyanine
(FePc) and C32H16FeN8. In the DRPPR process, a PDMS soft mold
was applied to pattern the insulated resist layer. After the PDMS
mold was imprinted onto the resist layer, the loading force was
gradually increased by a precise-controlled loading system. Then
the force was released to eliminate the mold distortion. In the last
procedure, the insulation resist layer was baked with a proper
loading force and an ICP etching process was used to wipe off
the residual resist in order to reveal the underlying conductive
substrate. On the other hand, a special NIL process without the
residual etching process demonstrates as well. In this process, a
hard Cr stamp was used to pattern the insulation resist layer.
The Cr stamp was made by the PECVD process and the following
EBL and ICP processes. The Cr patterns aimed to absorb exposure
UV light. After the stamp was imprinted on the UV-curable resist,
the Cr patterns could protect the residual from UV exposure. Next,
the uncured resist could be easily washed out by organic solvent,
revealing the underlying conductive substrate as well. The two
methods both successfully led to patterned conductive substrates.
To grow CNT arrays, a 100-nm-thick Cr layer was sputtered onto
the patterned conductive substrates. The aligned CNT arrays were
prepared on the patterned conductive substrates by pyrolysis of
iron phthalocyanine, C32H16FeN8, which contained both the metal
catalyst and the carbon source required for the CNTs’ growth.
The aligned CNT arrays grew on the patterned conductive sub-
strates are displayed in Fig. 17c.
Selective growth of CNT arrays on the substrates can be
achieved by using NIL as described above. Moreover, patterned
CNT arrays can also be obtained by a transferring method. Wang
et al. demonstrated a method to transfer and form aligned CNT
arrays using isotropic conductive adhesive (ICA) [99]. The process
was based on two main steps: NIL of the ICA and transfer of CNTs.
A pyramid-cavity Si mold made by anisotropic wet etching was
used to imprint the ICA. Before imprinting into the ICA, the Si mold
was coated with a thin layer of release agent in order to prevent
the ICA from sticking to the mold. In the first step, a drop of the
ICA was placed on a Si substrate and then imprinted by the mold.
The imprinting of the ICA was carried out by two steps. The ICA is
first imprinted under elevated temperature and high pressure.
Under the elevated temperature, the ICA became deformable and
thus easy to be patterned. The ICA was imprinted under a pressure

Fig. 17. Schematic illustrations of the (a) DRPPR NIL and (b) novel NIL without residual etching process. (c) SEM images of aligned CNT arrays grown in the patterned
conductive areas. Reprinted with permission from Ref. [98] (Copyright 2008 Elsevier Ltd.).
116 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119

force of 40 N at 60 °C for 90 s. Then the ICA was cured under 20 N
at 150 °C for 90 s. After demolding, pyramid-like structures were
formed on the ICA. Next, a heat transfer process was applied to
produce discrete ICA patterns. A target Si substrate sputtered with
a thin titanium/gold layer was brought contact to the patterned
ICA. After the two substrates are separated, an array of discrete
ICA patterns was transferred onto on the target substrate. To fabri-
cate CNT arrays, a substrate with CNT film was pressed onto the
chip carrying the ICA array under a pressure force of 20 N and a
temperature of 150 °C. Then the CNT arrays could be readily trans-
ferred onto the target substrate via the patterned ICA, and leave
cavities on the origin CNT film. Therefore, NIL can be used to fabri-
cate patterned CNT arrays by means of two methods, one is to pat-
tern the growing areas of CNT arrays, and the other one is to
transfer CNT arrays via the adhesive layer patterned by NIL.
5.2. Graphene
Nanopatterned graphene demonstrates an open bandgap while
graphene is originally a zero-bandgap material [100,101]. The
dimension of the nanostructured graphene is typically on the order
of less than 10 nm, thus a high-resolution patterning method is
required. As NIL is demonstrated as a high-resolution lithographic
method, NIL for patterning graphene has been developed accord-
ingly. In contrast to metal, ceramic or polymer materials, pattern-
ing graphene sheet cannot be achieved by directly imprinting
process due to its angstrom-scale thickness. Therefore, other NIL-
based processes were established. As demonstrated by Liang
et al., graphene nanomeshes (GNM) with sub-10 nm ribbon width
was obtained via the NIL [101]. To begin the patterning of graph-
ene sheet, graphene was firstly transferred onto a target substrate.
Next, an imprint resist was subsequently spin-coated on the graph-
ene. A hard mold with designed patterns pressed into the resist,
and plasma etching was carried out to remove the residual resist
as well as the underlying graphene on the imprinted region. After
the removal of the resist, a nanostructured graphene with a nega-
tive-replica pattern to the mold was obtained. The plasma etching
duration would determine the ribbon width of the GNM, and
therefore the ribbon width as well as the electronic state of the
GNM could be finely modified.
Using a pillar mold, graphene nanorings could be fabricated
by NIL as well [102]. The process is indicated in Fig. 18a–f. A

Fig. 18. Schematic illustration of the process flow for preparing graphene nanorings by NIL: (a) Nanoimprint on a three layer film (resist/PMMA/PVA) by a pillar mold, (b)
transfer of the hole patterns after releasing the mold, (c) plasma etching on the residual layer, (d) formation of Ni nanotubes by Ni deposition and the subsequent Ar plasma
etching, (e) removal of the Ni/resist/PMMA layer, and (f) O2 plasma etching on the PVA layer and graphene. The lift-off process of the PVA layer along with the Ni nanotubes
left the graphene nanorings. (g) SEM images of the as-fabricted graphene nanorings. Reprinted with permission from Ref. [102] (Copyright 2013 WILEY-VCH Verlag GmbH &
Co. KGaA, Weinheim).
 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119
three-layer film (resist/PMMA/PVA) was spin-coated on a graphene
sheet. After the pillar mold was imprinted into the resist, plasma
etching was carried out to remove the residual resist and transfer
the hole-array patterns to the underlying layers. As a result,
hole-array patterns with a diameter of 300 nm and a height of
420 nm were fabricated. A 30 nm-thick PVA residual layer was
deliberately left as a buffer layer, and Ni was deposited onto the
patterned layers subsequently. Then an Ar plasma etching was
used to convert the deposited Ni nanocups into nanotubes. The
substrate was then placed in acetone to remove the Ni/resist/
PMMA layers, and left the PVA layer with embedded Ni nanotubes.
In the last, O2 plasma was used to etch both the PVA layer and the
underlying graphene. Subsequently, the lift-off process of the PVA
layer along with the Ni nanotubes led to the patterned graphene
nanorings (Fig. 18g).
On the other hand, UV-NIL was proposed to fabricate large-area
micro- and nanostructured graphene in low cost. Bergmair et al.
demonstrated that the UV-NIL for patterning exfoliated as well as
CVD grown graphene that overwhelmed the thermal NIL or hot
embossing method by much shorter process times [103]. Besides,
the process was suitable for graphene transferred on versatile sub-
strates such as Ni, Cu, and SiO2 substrates. As the UV-NIL for other
substrates, the UV-NIL process for graphene was carried out by
pressing a mold into a UV-curable resist, and using UV light expo-
sure to harden the patterned resist. A following plasma etching
was applied to remove the residual resist layer and transfer the
patterns into the underlying graphene. However, the hardened
resist in UV-NIL was typically not soluble in organic solvents.
Therefore, how to remove the hardened resist without damaging
the underlying graphene layer was an important issue. Bergmair
et al. used a two-layer resist in their system. The bottom resist
acted as a transfer layer that prevented the damage of the pat-
terned graphene when removing the resist. By means of this
method, various patterned graphene structures could be obtained.
With a designed mold patterns, cruciform graphene with smallest
feature sizes down to 20 nm was achieved.
5.3. Metallic nanoparticles
Metallic NP arrays have been achieved by NIL involving lift-off
process. The metallic NPs or nanostructures are formed by the
NIL process. Here we focus on the NIL for patterning or transferring
colloidal metallic NPs, where the NIL was used to define the loca-
tion of chemically synthesized NPs [104,105]. The advantage of
using NIL to define the location of NPs is its high reproducibility.
Besides, the NP arrays could be obtained over a centimeter-scale
area in a single step, which overwhelmed the electron beam lithog-
raphy or photolithography.
For example, we have used the reversal NIL to prepare NP arrays
embedded in plastic substrates [104]. The as-prepared NPs were
first self-assembling on rigid substrates such as glass or Si. To pre-
pare embedded NPs in plastic substrate (PC here), the PC substrates
were brought into direct contact with the self-assembled metal
NPs on rigid substrates. The reversal NIL was carried out at various
temperatures near and below the Tg of PC substrates (150 °C)
under pressures in the range from 0.5 to 6 MPa. Under these
imprinting conditions, the NPs on the rigid substrates could be
pressed and embedded into the PC substrates easily due to the
drop in the modulus of PC substrates. The transferring of the NPs
determined on the adhesion force between the PC/NPs and rigid
substrate/NPs. Because the PC substrates were softened at elevated
temperatures, the adhesive force between PC and NPs was
enhanced and greater than that between the rigid substrates and
NPs. After demolding, the rigid substrates could once again adsorb
metal NPs and be reused in the imprinting process. Notably the
surface modification of the substrates was only needed during
117
the first time of metal NPs self-assembly. Moreover, the imprinting
conditions (e.g., temperature and applied pressure) determined the
final depth of the embedded NPs. Before imprinting, the NPs self-
assembled on the glass slide demonstrated a height (thus the
diameter of NPs) of 61 nm. When the imprinting process was fin-
ished, the depth of the embedded NPs was merely 20 nm under a
small imprinting pressure of 1 MPa. Interestingly, this result indi-
cated that the NPs could be transferred successfully to the PC sub-
strates even when the embedded depth was less than half of the
diameter of the NPs. When the pressure was increased to 3 MPa,
the embedded depth increased gradually to 54 nm. Additionally,
if the imprinting process was carried out at 6 MPa, the NPs
appeared to be completely buried under the PC surface. The tem-
perature largely influences the imprinting process as well. At
140 °C, the NPs were completely buried under the surface, even
when the pressure was only 1 MPa, presumably because of the
rapid drop in modulus of PC when the temperature reached the
heat deflection temperature (HDT), which was typically close to
its value of Tg. The HDT was the temperature at which a polymer
material deforms under a specified load. For PC, the HDT was
140 °C under a testing pressure of 0.455 MPa. Thus, the depth of
the embedded Au NPs into the PC surface could be finely modified
by changing the applied pressure when the temperature was
slightly below the HDT (e.g., 120 °C), and the embedded depth
was not easily controlled at the HDT (140 °C). Furthermore, the
imprinted PC surface would be too rough when the process was
performed at a temperature above the Tg of PC, as well as for other
polymer materials.
5.4. Applications of nanostructured nanomaterials
The CNT arrays have attracted great interests in the application
of field emission display (FED), sensor devices, electrochemical
energy storage and flip-chip bumps. Therefore, CNT arrays pat-
terned by NIL have wide applications. For example, the field emis-
sion properties of the aligned CNTs patterned by NIL were tested,
as demonstrated by Ying et al. [98].
The nanostructured graphene sheet can be applied on, for
example, field effect transistors (FETs) [101]. Electronic character-
ization of GNM-based FETs was performed. When the average rib-
bon-width decreased, the ON/OFF current ratio of devices
increased. The ratio would achieve close to 100 when the width
was less than 10 nm. The results implied that an electronic band-
gap was formed in GNMs. Accordingly, the bandgap value inversely
scaled with the average ribbon width of GNMs. Therefore, con-
structing nanostructured graphene would benefit the electronic
applications of graphene, and determined which superlattices of
graphene structures could be obtained. It has proved that NIL is
an efficient method to prepare nanostructured graphene sheet
with critical dimensions.
The NPs embedded in PC plates prepared by reversal NIL could
be applied as a SPR scattering sensor [104]. As mentioned above,
the imprinting temperature and pressure would influence the
depth of embedded NPs, and thus the scattering ability of the sen-
sor. For example, the higher imprinting temperature and applied
pressure would result in a deeply embedded NPs, and more dense
NP arrays. However, completely embedded NPs were not able to
bind to the target molecules. Therefore, optimal imprinting condi-
tions were necessary to the fabrication of SPR scattering sensors
exhibiting both strong scattering power and large naked surfaces
to interact with target molecules. To fabricate the SPR scattering
sensor, hollow gold NPs (HGN) were transferred on to PC plate at
110 °C under 0.5 MPa. The scattering wavelength of the HGN-mod-
ified PC plate demonstrated a distinguishable red-shift before and
after binding 1-hexadecanethiol, revealing the sensing ability of
the SPR scattering sensor. The detection of thiol-containing amino
118 C.-C. Yu, H.-L. Chen / Microelectronic Engineering 132 (2015) 98–119
acids such as cysteine (Cys) has been demonstrated on the SPR
scattering sensor. The surfaces of NPs embedded in PC plate were
modified with Cys-NP target molecules with a tree-step method.
The scattering wavelength of the SPR scattering sensor displayed
a red-shift from 585 nm to 590 nm before and after binding target
in the presence of 1 mM Cys. Besides, a new SPR scattering peak
was revealed at 745 nm. The long-wavelength SPR scattering peak
was due to the plasmonic coupling between the NPs embedded in
PC plate and the NPs on Cys-NP target molecules. By quantifying
the scattering power ratio of 745 nm to 585 nm, a linear detection
of Cys concentration from 103 M to 106 M was obtained.
6. Conclusions
Nanostructured functional materials exhibiting unique proper-
ties have been demonstrated many applications on modern
devices. Traditionally, nanostructured functional materials are pat-
terned by electron beam lithography or photolithography. To over-
come the cost and throughput issue in conventional lithography
methods, NIL is developed as an alternative method for patterning
various materials. Depending on the target materials, versatile NIL
methods have been proposed and shown a superior texturing abil-
ity in nanoscale. NIL based techniques have been carried out to pat-
tern metals, ceramics, plastics, and nanomaterials. Since metals are
ductile materials, the direct patterning of metals by NIL is applica-
ble. Besides, a solid state electrochemical stamping has been devel-
oped as another choice for patterning metals. Imprinting-based
transfer of metallic patterns (nanotransfer printing, reversal NIL,
and template stripping) are proposed to manufacture versatile
3D metallic structures, which reveal unique plasmonic properties.
These metallic nanostructures are potentially adopted in optoelec-
tronic devices. Based on previous literatures, these devices showed
a comparable or ever better performance than that made by con-
ventional lithographic methods. On the other hand, NIL for brittle
ceramic materials is fulfilled. Besides using dry etching, a sol–gel
process is widely adopted in NIL. Various ceramic patterns are
developed, and these nanostructured ceramic can act as the sup-
ports for optoelectronic devices such as LEDs. Moreover, reversal
NIL for pattering ceramic has been proposed as well. By repeating
the imprinting process, multilayered 3D ceramic structures are
obtained. On the other hand, flexible plastic materials are suitable
for R2R NIL process. Due to the material property of plastic, the
temperature is a critical factor in the NIL for plastics. By finely con-
trolling the imprinting parameters, patterning plastic materials is
achieved in high throughput. Designs of the roller systems and
the transporting speed of the plastic film also influence the final
features of imprinted plastic. In the last, nanomaterials including
carbon nanotubes, graphene, and metallic nanoparticles are pat-
terned by NIL. These patterned nanomaterials find superior proper-
ties on field emission devices, field effect transistors, and sensors.
Overall, we hope this review of NIL for functional materials will
inspire more next-generation devices to be developed by NIL, with
versatile choices of imprinting processes and materials.
Acknowledgements
We thank the Ministry of Science and Technology, Taiwan, for
supporting this study under contracts 103-2221-E-002-041-MY3
and 103-2221-E-002-092-MY3.
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