Nano Today 37 (2021) 101063

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Nano Today
journal homepage: www.elsevier.com/locate/nanotoday

Review

Vertically aligned nanostructures for a reliable and ultrasensitive

SERS-active platform: Fabrication and engineering strategies ]]
]]]]]]
]]

⁎ ⁎⁎
Yang Liu a,b, , Minjoon Kim b, Seunghee H. Cho b, Yeon Sik Jung b,
a
School of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, 333 Long Teng Road, Shanghai 201620, China
b
Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu, Daejeon 34141,
South Korea

a r t i cl e i nfo a bstr ac t

Article history: Surface-enhanced Raman spectroscopy (SERS) is a powerful cross-disciplinary analytical technique
Received 11 August 2020 allowing ultrasensitive detection of various analytes with a fingerprint-like characteristic, even down to
Received in revised form 16 November 2020 the single-molecule level. One of the key issues for SERS-based trace applications is the rational design
Accepted 20 December 2020
and fabrication of structurally uniform substrates with high sensitivity, stability, and good signal
Available online 13 January 2021
reproducibility. Low-dimensional SERS-active nanomaterials are increasingly facing many challenges
and cannot meet these requirements. In recent years, due to developments in nanofabrication and an
Keywords:
Surface-enhanced Raman spectroscopy improved knowledge of plasmonic properties of nanomaterials, significant progress has been made in
Ultrasensitive detection the area of complex nanostructures with ordered architectures, elemental compositions, and controlled
Ordered architectures plasmonic properties, which are critical for ultrasensitive, uniform, reliable, and reproducible
Vertically aligned measurements. In this review, the fabrication methodologies and classification of vertically structured
Hot spots nanoarchitectures are outlined. Subsequently, the morphological and geometrical effects on SERS
Enhancement performance are discussed based on the substrate materials. Insight into advanced engineering strate­
gies towards some SERS-active nanostructures is supplied in this context. Finally, the challenges and
future directions are pointed out for the development of vertically nanostructured SERS substrates and
their ultrasensitive sensing applications.
© 2020 Elsevier Ltd. All rights reserved.

Contents

. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
. Fabrication methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
. Top-down nanofabrication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
. Bottom-up nanofabrication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
. Types of vertically aligned SERS substrates. . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
. Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
. Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
. Zinc oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
. Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
. CNTs and graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
. Biomaterials and biomimetic structures . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
. Structure engineering and probe sensing strategies towards ultrasensitive detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
. Uniquely designed nanostructures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
. Surface-energy engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
. Capillary force-driven leaning nanostructures . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
. Potential applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

⁎
Corresponding author at: School of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, 333 Long Teng Road, Shanghai 201620, China.
⁎⁎
Corresponding author.
E-mail addresses: [email protected] (Y. Liu), [email protected] (Y.S. Jung).

https://doi.org/10.1016/j.nantod.2020.101063
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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

. Conclusion and future perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

. CRediT authorship contribution statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
. Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
. Acknowledgements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

Introduction blocks have been designed and developed over the past decade
[11,12,15], including substrates consisting of colloidal nanoparticles,
Raman spectroscopy has become a popular analytical technique nanowires or nanorods, nanoplates, etc. The substrates comprising
for the detection and structural analysis of molecular materials. low-dimensional nanostructures, however, still face several chal­
However, one of the critical limitations of Raman analysis is related lenges including low structural uniformity, inhomogeneous dis­
to the inherent weakness of Raman signals. Surface-enhanced tribution of hot spots, low sensitivity, and poor reproducibility of
Raman spectroscopy (SERS), in contrast, is a well-established tech­ SERS signals.
nique that amplifies Raman signals of analytes by multiple magni­ For practical and dependable applications, an effective SERS
tude orders. SERS has attracted enormous attention since its substrate should not only be designed with enormous hot spots to
discovery because of its ultrahigh sensitivity, rapid response time, guarantee greater sensitivity, but also the hot spots should be dis­
and non-destructive molecular analysis with fingerprint-like char­ tributed uniformly to achieve good signal reproducibility. The advent
acteristic signals. These features have triggered the application of and exploration of complex nanoarchitectures containing periodic
SERS in many fields such as analytical chemistry, biomedical diag­ plasmonic structures, e.g., vertically aligned nanostructures (Fig. 2),
nostics, environmental analysis, materials science, forensic science, has thus become a dominant trend to obtain the desired SERS-active
and so on [1]. substrates featuring sufficiently high hot spot densities. Compared
The discovery of SERS can be traced back to the 1970s when in­ with planar substrates, the remarkable advantages of this kind of
tense Raman signals from pyridine adsorbed on the rough surface of substrate are as follows: (i) ordered/periodic arrangement of struc­
an Ag electrode were observed by Fleischmann et al. [2], while Van ture in a long-range; (ii) structural parameters controllable to opti­
Duyne defined “SERS” as a Raman enhancement effect that origi­ mize SERS signals by altering output condition; (iii) extended SERS
nates from the surface of noble metals [3]. Subsequently, Creighton, hot spots three-dimensionally (3D) along the z-axis; (iv) large sur­
Moskovits et al. [4,5] proposed two mechanisms to explain the en­ face area beneficial for target analytes adsorption; and (v) excellent
hancement of Raman signals: electromagnetic and chemical me­ structural stability and reliability for uniform and reproducible SERS
chanisms. The electromagnetic (EM) mechanism [6] primarily signals.
results from amplification of an electric field by excitation of loca­ There has been significant work to design, fabricate, and utilize
lized surface plasmon resonances (LSPR) of the SERS-active under­ plasmonic nanostructures and nanoarchitectures by top-down and
lying material. The chemical enhancement (CE) mechanism bottom-up approaches. These novel structures include vertically
meanwhile is associated with charge-transfer [7,8]. In order to aligned metal or metal-decorated nanowire, nanopillar, and nanorod
evaluate the signal enhancement, an enhancement factor (EF) is arrays (Fig. 2a–d), in either porous or non-porous form. Besides
used and is normally defined as the ratio of the normalized SERS these vertical-aligned traditional arrays, unique nanostructures such
signal to the normal Raman signal of the same molecule [9]. This as multi-stacked nanowires, lamellar gratings, nanotowers, and gy­
enhancement can also be calculated with computational methods roid nanoarchitectures (Fig. 2e–h), elevated nanostructure arrays of
such as finite-difference time-domain (FDTD) simulations [10]. It is nanotriangles, nanobowties, and nanostar arrays (Fig. 2i–k), clus­
now generally agreed that the EM mechanism contributes dom­ tered nanopillar arrays (Fig. 2l), etc., have also been developed in
inantly to most SERS processes. The enhancement mechanisms of recent years. These outstanding SERS substrates provide strong hot
SERS effects have been broadly explored and summarized in several spots in a large density within the laser illumination area, such as
excellent reviews [6,8,9,11–15]. Metal nanostructures, particularly nanopores or interconnected helices, stacked cross-point or ridges,
Ag and Au, can be used as plasmonic antennas to enhance the Raman multiple branches or sharp protrusion, and so on.
signals for SERS-based molecular detection. The local EM field due to In this review, we outline the past and current fabrication
plasmon excitation is normally largest at crevices, nanogaps, or methodologies of the vertically structured SERS-active sensing
sharp tips in nanostructures [13,15,16], also known as hot spots. platform, presenting a systematic classification and discussion based
Raman scattering signals of various molecules placed in close vici­ on the types of SERS substrates using different materials, including
nity to the hot spots can be dramatically amplified (Fig. 1a). Si, zinc oxide (ZnO), polymers, carbon nanotubes (CNTs), and bio-
As nanofabrication has progressed in recent years and the plas­ based nanoarchitectures. Their morphological and geometrical ef­
monic properties of nanomaterials have gained greater under­ fects on SERS performance, such as size, shape, pattern density, and
standing, SERS-based sensing platforms have been applied to trace- distribution, are also discussed. In addition, an overview of recent
molecule detection even down to the single-molecule (SM) level developments in engineering strategies toward SERS-active nanos­
[9,16]. In 1997, Nie and Emory [17] and Kneipp et al. [18] both re­ tructures is also presented. Finally, we conclude and provide an
ported SM detection of resonant dyes by SERS. Ultrasensitive de­ outlook on advances in nanostructured SERS substrates and their
tection of chemicals and biological analytes has become crucial ultrasensitive sensing applications in the future.
especially in trace-amount or SM level concentrations in various
scientific fields [19–23], including food and pollutants monitoring, Fabrication methods
chemical identification, biological sensing, homeland security, etc.
However, the critical issue in SERS-based trace-amount detection is With the development of nanotechnology, sensitive, efficient,
a reasonable design and fabrication approach for structurally uni­ reproducible, and uniform SERS-active substrates have been fabri­
form SERS substrates that satisfy all of the following requirements: cated through diverse chemical synthesis and nanofabrication
high sensitivity, good stability, and good signal reproducibility methods. Nanostructured SERS substrates have been created using a
(Fig. 1b). Therefore, SERS substrates based on a variety of building range of techniques, which are usually classified as top-down and

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

Fig. 1. Plasmonic nanogap structures with ultrasmall nanogaps and plasmonic nanogap-enhanced Raman scattering. (a) Highly enhanced electromagnetic (EM) fields in the 1 nm
gap of a dimer and surface-enhanced Raman scattering (SERS) from a dimeric nanostructure. (b) Challenges in generating narrower distributions of larger SERS enhancement
factors. Copyright 2016, American Chemical Society.
Adapted with permission [13].

Fig. 2. Schematic illustrations of representative vertically structured nanoarchitectures as SERS substrates. Vertically aligned arrays of (a) Au nanorods assembled on a smooth
substrate. Vertically aligned arrays of (b) Si nanopillars, (c) ZnO nanowires, and (d) CNTs as scaffolds for metal deposition. Multi-stacked nanostructures of (e) metal nanowires on
a smooth substrate, (f) lamellar grating nanostructures, and (g) nanotower arrays. (h) unique gyroid nanoarchitecture. Elevated arrays of (i) hexagonally ordered triangular plates,
(j) nanobowties, (k) nanostars, and (l) clustered nanopillar arrays.

bottom-up methods. Top-down methods such as lithography and lithography and maskless lithography. Photolithography (PL) is a
etching are subtractive processes that involve the reduction of pre- commonly adopted mask-based lithography that uses ultraviolet
existing materials or structures. In contrast, bottom-up methods are (UV) light for “printing” a pattern of a predefined mask or reticle
usually additive, involving direct growth or self-assembly. In general, onto a photoresist through contact, proximity, or projection ex­
top-down methods generate nonmetallic structures that require posure. The photoresist patterns are usually removed after exposure
further metallization, while bottom-up methods are mainly em­ and subsequent processing steps (Fig. 3a). A critical challenge in PL is
ployed to fabricate metallic aligned structures. In this review, we the limited resolution of patterns, which is usually inadequate for a
mainly focus on the techniques that are available for the fabrication high SERS enhancement effect [24]. Therefore, many other mask-
of vertically aligned SERS-active nanostructures. based strategies have been developed to improve the pattern re­
solution, and PL can sometimes be employed in combination with
Top-down nanofabrication these strategies. One of them is nanosphere lithography (NSL) [25].
Colloidal solutions of monodisperse spherical particle materials such
Lithography-based patterning techniques are critical top-down as silica (SiO2) and polystyrene (PS) are used to assemble well-or­
methods that can be classified into two categories: mask-based dered close-packed monolayer arrays when dried on a surface

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

Fig. 3. (a) Schematic top-down fabrication of Si pillar arrays involving photolithography, nanosphere lithography, and metal-assisted chemical etching. (b) SEM images of vertical
Si (100) nanopillar arrays obtained through DRIE with an antireflection coating etch mask. Copyright 2008, IOP Publishing Ltd. (c) SEM images of Si nanopillar arrays obtained after
BCP masking and etching. Copyright 2016, American Chemical Society. (d) Schematic of DRIE etching process. (e) SEM image of Si pillar arrays with square and hexagonal
arrangements. Copyright 2017, Royal Chemical Society. (f) Periodical Si array fabricated by e-beam lithography. A single micropillar combined with plasmonic nanocones and
gratings was fabricated using FIB milling. Copyright 2011, Macmillan Publishers Limited. (g) Schematic diagram of experimental set-up for phase-shift interference and SEM
images showing bare and Ag-deposited stacked-disk nanotower arrays. Copyright 2015 and 2016, Wiley-VCH. (h) Geometry of a single prism and resulting beam configuration.
Simulation and SEM images of the resulting woodpile structures are also shown. Copyright 2012, Royal Chemical Society.
(b) Adapted with permission [38]. (c) Adapted with permission [37]. (e) Adapted with permission [39]. (f) Adapted with permission [40]. (g) Adapted with permission [41,42]. (h)
Adapted with permission [43].

[26–33]. Such colloidal close-packed arrays can be used as masks to process. Metal-assisted chemical etching (MaCE) is a representative
transfer array patterns onto surfaces via post-modifications such as wet etching method on Si (Fig. 3a). Anisotropic and isotropic etching
etching and photo exposure (Fig. 3a). The size and spacing of the on patterned single crystal Si is possible when using, for instance,
resulting array patterns can be determined by the control of the KOH [44] and HF + H2O2 [27–29], respectively. Dry etching is a
original colloidal particle diameter or by adjustment in post-treat­ plasma-involved physical process (etched by inert ions such as Ar+),
ment. Another commonly used self-assembled mask for nanofabri­ a chemical process (etched by ions, radicals, etc.), or a combination
cation is anodic aluminum oxide (AAO). AAO contains a close-packed of both physical and chemical processes (ion bombardment plus
array of nanoscale channels, which are prepared by electrochemical chemical reaction). Deep reactive ion etching (DRIE), also called the
anodization of Al. This close-packed nanochannel array can act as a “Bosch process” [39,45–47], is a representative dry etching process,
mask, which has a similar role to that of packed colloids [34]. as shown in (Fig. 3d–e).
Moreover, molecular self-assembly that uses block copolymers While mask-based lithography is a facile process to fabricate
(BCPs) can also be exploited to create masks for nanopatterning. highly ordered periodic nanostructures with desired patterns, it is
BCPs are molecules consisting of two or more dissimilar polymer also possible to directly draw fine features without masks. Except for
chains that undergo “microphase separation” into ordered nanoscale e-beam lithography (EBL), most maskless lithography methods are
domains under certain conditions, such as molecular parameter of direct-writing processes that do not require etching. In EBL, an ac­
BCP or external annealing conditions. The assembled nanodomains celerated and focused beam of electrons is directly exposed onto an
can be selectively etched into nanopatterns for use as masks for the electron-sensitive resist surface to write high-resolution patterns.
creation of well-ordered patterns [35]. For example, by using EBL techniques combined with appropriate etching methods are
directed self-assembly of polystyrene-b-polymethylmethacrylate highly controllable and reproducible to fabricate uniformly nanos­
(PS-b-PMMA) as the etching mask, Yeom and colleagues fabricated tructured SERS substrates with high performance. However, in
various vertically aligned Pt nanostructures including Pt nanoholes, general, it is not simple to manufacture sub-20 nm feature sizes on a
nanorods, and nanotubes [36]. To manufacture highly ordered and macroscopic area [48], thus limiting their practical applications.
dense Si nanostructures [37], Wu and Li employed polystyrene- Similar to EBL, a focused ion-beam (FIB) can also be used for direct-
block-polydimethylsiloxane (PS-b-PDMS) as a mask and directly writing lithography. Typically, using gallium ions (Ga+), it can locally
etched it without using any intermediate layer or incorporating etch away materials into desired patterns. Feature sizes below 10 nm
external precursors (Fig. 3c). have been demonstrated (Fig. 3f) [40]. However, the high-cost and
To fabricate vertically aligned SERS-active nanostructures, mask- time-consuming process limits its applications and widespread use.
based lithography should be combined with etching treatment to Recently, interference lithography (IL) has been widely investigated
sculpture the patterned substrates. Etching refers to the surface due to its simple and reproducible production procedures [49]. Kim
modification of lithographically patterned materials by applying wet et al. reported a phaseshift IL method to produce vertically aligned
or dry etchants and is usually classified into wet or dry processes. nanotower arrays [41]. In the lithography process, a nanostructured
Target materials are dissolvable in an etchant solution in the wet grating containing a square array of periodic posts was employed. A

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

Fig. 4. (a) Comparison of the current imprinting techniques in terms of processing temperature, materials, resolution, and strain rate. Copyright 2014, American Association for
the Advancement of Science. Schematic processes of (b) nanoimprint patterning, (c) electrochemical deposition, (d) colloidal coating.
(a) Adapted with permission [64].

laser beam (325 nm wavelength) was impinged on the grating and PAN, PMMA, and PC nanopillar arrays were easily obtained by thermal
the derived diffraction beams were repeatedly produced along the imprinting while PS and PE nanotube arrays can be prepared by melt
propagation direction of incident light. If the photoresist parameters wetting. Furthermore, the employed stamp molds are generally peeled
and underlying substrates are controlled in ways such as by using a off after replication, while wet chemical etching is an optional strategy
dielectric mirror [42], the propagating interference beam would be to remove the AAO template [59,62,63].
reflected back into the resist. This results in a standing wave via Although the top-down methods described above provide useful
additional interference between the two beams, and the nanos­ tools for patterning and creating nanoscale features, they have dif­
tructure could then be deliberately tailored into desired patterns ferent strengths and weaknesses. Most of the fabricated archi­
(Fig. 3g). If the above grating is changed into a prism, holographic tectures are SERS-inactive materials, which need further decoration
lithography (HL) can be achieved through the optical interference of with SERS-active metals to create plasmonic structures before ap­
coherent light beams [43,50]. Yang’s group demonstrated that prism plication in ultrasensitive detection. However, the metallization
HL is a fast and easy method to build large-area periodic 3D na­ process is also sometimes suitable for structural amendments to
nostructures and predetermined highly porous architectures create narrow nanogaps [65]. Several metal deposition techniques
(Fig. 3h) unachievable by other techniques [43]. are available depending on the material and process requirements,
In addition, nanoimprint lithography (NIL) has been extensively and they can be broadly divided into solution-phase and vapor-
used to replicate highly periodic SERS-related nanostructures on large phase approaches. Solution-phase deposition approaches include
areas with relatively low costs (Fig. 4a). This is a template-assisted electrochemical deposition [39,51], electroless plating [26], electro­
approach (Fig. 4b) where the templates normally possess well-confined phoresis [66], and some colloidal coating techniques [27,67]. Elec­
voids in the form of channels, pores, or connected hollow spaces. AAO, trochemical deposition [68], also called electroplating, is a process
pre-lithographed Si molds [51,52], and daughter molds replicated from that requires an external current source while electroless plating is a
them [53] are frequently used stamping molds to fabricate inexpensive method where a chemical process supplies the required electrons
3D polymer arrays. The process generally involves the following pro­ (Fig. 4c). In addition, electrophoresis describes the migration of
cedure: 1) The surface of the mold is functionalized with an ultrathin charged colloidal particles or molecules induced by an electric field.
polymeric monolayer to reduce the surface energy between the mold In colloidal coating (Fig. 4d), spin-coating, spray-coating, and dip-
and applied polymers [54]; 2) solid patterns form inside the pores with coating are widely used methods due to their easy handling and fast
external stimuli such as UV irradiation, replicating the shape of the production properties, but lack reproducibility. The vapor-phase
void space in stamping mold; and 3) aligned structures are obtained deposition approach, for instance physical vapor deposition (PVD), is
after removal of the stamp scaffold. Light sensitive polymers such as the most commonly used approach. It uses physical phenomena
PUA [55], NOA61 [56], NXR2010 [57], and cyclic olefin copolymer [58] such as heating-induced evaporation or plasma-based ion bom­
are favored during the replication process assisted by UV light or lasers. bardment on a source substrate under vacuum conditions. Overall,
Mechanical or thermal treatment, however, can be performed during the methods available for metallization are wide and varied.
replica formation when the applied polymer is not responsive to UV
stimulus. In this case, polymers that possess low glass transition Bottom-up nanofabrication
temperatures are preferred, such as polyacrylonitrile (PAN) [51,52],
polymethylmethacrylate (PMMA) [59], polycarbonate (PC) [60], PS [53], As mentioned above, bottom-up methods are additive nanofab­
Polyamide (PA) [61], and polyethylene (PE) [62], to easily fill the empty rication approaches. Unlike top-down methods that mainly generate
regions of the mold. Vacuum or pressure assist is needed in some cases. nonmetallic structures and require additional metallization, bottom-

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

up methods are usually employed to directly fabricate metallic formed metal nanostructure before decomposing AAO [79]. None­
aligned structures. Examples are electrodeposition of vertically theless, it is possible to pre-load a conductive substrate onto AAO
aligned metal nanorods, self-assembly of Au nanorods (Au NRs), etc. with the help of an ultrathin polymer adhesion layer as both a
However, vertically aligned ZnO and CNT arrays, as scaffolds for SERS working electrode and rigid support [81]. Using this strategy, SERS-
substrates, are among few pathways available for direct growth of active metal nanostructure arrays are easily obtained after electro­
vertical nanowires in a bottom-up fashion. They can be grown chemical deposition.
through a two-step process: seed generation and arrays formation. Self-assembling anisotropic supercrystals into a diverse range of
In the case of ZnO, spin-casting zinc acetate sol on substrates fol­ ordered superlattices have become an attractive bottom-up strategy
lowing by thermal decomposition [69] is a commonly used ZnO seed due to their operability and cost-effectiveness [82–84], these su­
introduction method, while direct-casting of prefabricated ZnO percrystals include nanorods [85–87], nanooctahedra [88,89], na­
seeds [70,71] and physical deposition of a ZnO source on substrates nocubes [90,91] and so on. Recent research showed that vertical
[72] are relatively straightforward approaches. In addition, dewetted noble metal nanorods arrays, for instance Au-based vertically
Au particles can serve as a seed to grow ZnO [73]. Owing to the standing arrays or closely packed horizontal arrays along vertical
flexible seed introducing strategies, ZnO nanoparticle-based ink direction [92], can be directly used as SERS substrates for ultra­
could be printed as seed layers by a screen-printing method [71]. sensitive detection. Au NRs are regarded as good plasmonic mate­
After seed formation, 3D ZnO arrays can be prepared through a rials for self-assembly due to their simple synthesis procedures,
hydrothermal method or even electrochemical deposition if the tunable surface energy for assembly, superior chemical stability, and
substrate is conductive. Here, zinc nitrate and amine sources such as extremely strong local EM fields from coupling with adjacent Au NRs
hexamethylenetetramine (HMTA), methenamine, diethylene­ [93]. Various strategies for Au NR assemblies have been reported, but
triamine, and polyethylenimine (PEI) are used during vertical ZnO droplet evaporation induced self-assembly (EISA) has proven to be a
growth processes [71,72,74]. The morphology of cone-shaped verti­ simple and convenient approach [82].
cally grown ZnO nanoarrays by a hydrothermal method is usually By controlling the rod parameters, colloidal concentration, or
limited, but is adjustable when using the chemical vapor deposition evaporation conditions, it is possible to induce the assembly of
(CVD) method. Ko and coworkers reported that the partial pressure spatial arranged Au NRs [94,95]. However, the surface chemistry of
and reactant amount affect the axial growth rate of ZnO [73]. A fast the assembling blocks plays an important role. The high positive
axial growth rate results in the formation of ZnO nanorods (ZnO charge created by the cetyltrimethylammonium bromide (CTAB)
NRs) and cone-shaped ZnO nanocones (ZnO NCs). The cone-shaped double layer on the Au NR surface induces a strong short-range re­
ZnO NCs can further be converted into ZnO nanonails (ZnO NNs) pulsion between neighboring rods, which should be overcome to
with an excess Zn powder source. allow packing of Au NRs into vertical superlattices [82]. Surface
ZnO can be formed on either flat or patterned substrates. Flat functionalization of Au NRs with specific ligands has been proposed
substrates are usually indium tin oxide (ITO), Si wafers, plastic in this respect (Fig. 5a). For example, to achieve anisotropic self-
substrates or graphite sheets, while patterned substrates are vari­ assembly of Au NRs in a centimeter-level, Chen and collaborators
able. Fan and colleagues rationally designed and fabricated highly selectively functionalized different facets of Au NRs with poly­
ordered treelike Si/ZnO hierarchical nanostructures using a combi­ ethylene glycol (PEG) [92]. The side-PEGylated Au NRs formed
nation of two common techniques: PL-assisted Si nanopillar wafer- tightly packed horizontal arrays, while the end-PEGylated Au NRs
scale manufacturing and bottom-up ZnO NR hydrothermal growth formed vertically arranged arrays on the substrate (Fig. 5b–c). By
[75]. Jang et al. fabricated hierarchically patterned ZnO nanos­ introducing rhodamine 6G (R6G) to adsorb onto CTAB partially-
tructures via IL and hydrothermal methods [76], while Li and col­ covered rods, Liu and collaborators realized an unexpected tetra­
leagues fabricated urchin-like ZnO hollow nanosphere arrays by gonal superlattice of the nanorods (Fig. 5d) [96]. In another
employing simple NSL before solution processes [74]. Due to the
light trapping effects achieved by these hierarchically patterned ZnO
nanostructures fabricated by a combination of multi-structural ap­
proaches, broadband absorption of light leads to Raman en­
hancement.
In the case of vertically aligned CNT (VACNT) arrays, the direct
growth process is relatively easy. Metal seeds can be generated from
thermal annealing of corresponding thin metal films, which are
usually deposited on Si substrates [77]. VA-CNT arrays can be ob­
tained when these catalyst substrates are subsequently im­
plemented in a CVD process. The average areal number density of
catalyst islands is approximately equal to that of CNTs. That is, the
direct growth method provides another alternative approach for the
concise fabrication of vertically aligned arrays, particularly ZnO
and CNTs.
Additional bottom-up methods for producing vertically struc­
tured arrays have also been developed. Electrochemical deposition
of SERS-active metals is a simple and popular method, but the
process requires templates to obtain metallic arrays. The AAO tem­
plate is mainly used in this method due to its highly ordered cy­
lindrical pores with size tunability, uniformity, and high density in
addition to easy removal capability after deposition of metals
(Fig. 4c). Most electrochemical deposition processes have demon­
strated the preparation of metal nanopillars [65], nanowires [78],
Fig. 5. (a) Surface functionalization of Au NR with specific ligands. Precisely
nanorods [79] and nanotubes [80]. In most cases, a working elec­ controlled self-assembled Au NR structures: (b) vertically aligned hexagonal Au NR
trode (commonly a thin Au layer) is formed at one face of the arrays, (c) horizontally aligned Au NR arrays, (d) vertically aligned tetragonal Au NR
double-pass AAO and post-loaded on a platform to support the arrays, and (e) horizontally aligned Au nanoarrow arrays.

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

approach, Yu and coworkers implemented exchange between the Types of vertically aligned SERS substrates
capping ligand CTAB and (11-mercaptoundecyl)hexa(ethylene
glycol) (MUDOL) to achieve macroscopic 3D plasmonic superlattice Metals
arrays composed of dense and nearly vertically aligned Au NRs [97].
Recently, Qi et al. prepared Au nanoarrows consisting of two pyr­ Numerous studies have shown that nanostructures of coinage
amidal heads by controlled overgrowth of Au NRs, which were se­ metals (mostly Ag and Au) as plasmonic antennas can generate
lectively passivated by cetyltrimethylammonium chloride (CTAC) greater EM enhancements than transition metals. This is due to
[98]. The Au nanoarrows showed distinct packing and interlocking coinage metals’ LSPR, or light-driven coherent oscillations of excited
ability and allowed for shape-directed assembly due to their distinct conduction electrons [104]. The EM field enhancement is especially
concave geometry (Fig. 5e). In addition to the self-assembly of ani­ high at sharp tips, corners, and inter-gaps between nanorods, pillars,
sotropic nanorods, 3D assembly of metallic nanoparticles is also a and nanopores [83]. These are typically referred to as hot spots that
representative bottom-up method. For instance, 3D flower-like ar­ enhance the Raman scattering of molecules in those regions.
chitectures with abundant petals can be formed from charged Aligned Au NRs are very good SERS-active nanostructures,
aerosols [99], induced by an ion-induced electrostatic force focused especially due to their tunable optical characteristics and superior
in a controlled manner. chemical stability [83,105]. The fields are limited to gaps between
It is worth mentioning that layer-by-layer stacking of aligned 1D neighboring Au NRs to produce extremely high near-field localiza­
metal nanostructures is an emerging bottom-up method for con­ tion in spatial structures. Recently, assembling monodisperse ani­
structing metallic structures with multiple small gaps [100]. A ty­ sotropic Au NRs into ordered arrays has attracted increasing interest
pical example is the nanotransfer printing (nTP) strategy, which is a [82]. The gaps among the assembled nanorods can trap liquid ana­
recently developed nanofabrication technique to controllably build lytes because of the capillary force [93], and Raman scattering of the
3D nanostructures on arbitrary substrates including flexible plastic target analytes is enhanced by the strong localized EM fields, leading
or non-planar surfaces [101]. The printed nanostructures generally to ultrasensitive detection. Several self-assembled vertically aligned
possess excellent uniformity, making it possible to obtain uniform Au NRs ordered arrays, for example, vertically standing Au NRs or
and reproducible SERS signals. The nTP technique usually consists of vertically aligned multilayers of horizontal Au NRs, are introduced in
several steps: nanostructured replica preparation, metal deposition, the Fabrication Methods section. It is particularly worth mentioning
and transfer of the nanostructured metals onto new substrates [101]. the representative study by Xiong and colleagues on assembling
Zhang and colleagues successively built novel 3D nanogap arrays via vertically aligned monolayer of Au NRs (Fig. 7a) [93]. The distance
a unique transfer printing and stacking procedure (Fig. 6a), which is between the adjacent Au NRs, with 0.8 nm nominal gap, was tuned
hard to achieve by conventional nanofabrication methods [102]. by adjusting the ionic strength. The electrostatic and van der Waals
Furthermore, Jeong et al. demonstrated vertically stacked, large area interaction govern the formation of vertical arrays (Fig. 7b), and a
3D cross-point plasmonic nanostructures through a sequential decrease in gap distance improves the EF and the SERS sensitivity
transfer printing technique (Fig. 6b) [103]. nTP is a promising ap­ (Fig. 7c–d).
proach for use when the application of conventional nanofabrication However, for the assembly of Au NRs, many targets should still be
techniques is challenging. met, such as defect-free property/homogeneity of assembled verti­
In short, a number of top-down and bottom-up methods have cally aligned Au NR superstructures, large scale producibility, and
been successfully established for the fabrication of ordered vertical process controllability [92]. In particular, organic capping ligands on
nanostructures, which are favorable for ultrasensitive application by Au NR as stable reagents in a typical self-assembly procedure often
SERS. Both top-down and bottom-up methods have respective ad­ prevent the hot spots from being accessed by target analytes and
vantages and disadvantages. By an appropriate combination of therefore suppress the SERS activity [106]. Therefore, the main
bottom-up and top-down techniques, one can create a SERS active challenge is to reproducibly fabricate stable SERS substrates with
nanostructure that uses exploits advantages and avoids the draw­ uniform hot spots and possibly push the gaps to the sub-nanometer
backs of each applied fabrication technique. Therefore, researchers range to enhance sensitivity.
have more flexible and feasible options for the desired nanofabri­ One promising approach to solve these problems is to fabricate
cation. ordered metal nanorod arrays using templates with highly dense

Fig. 6. (a) Schematics of the process of fabricating size-tunable 3D nanogaps based on 2D nanogap arrays. Copyright 2016, Wiley-VCH. (b) Schematic procedure for the fabrication
of 3D cross-point plasmonic nanostructures. Copyright 2016, Wiley-VCH.
(a) Adapted with permission [102]. (b) Adapted with permission [103].

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

Fig. 7. (a) Illustration and SEM images of a vertical Au NR monolayer arranged in a hexagonal lattice. The edge-to-edge gap distance is 7.7 ± 0.4 nm. (b) Theoretical calculation of
interaction free energy as a function of the gap distance between two Au NRs where the Debye length k-1 is 3 nm. (c) Local electric field enhancement factor, |E/E0|4, in the cross
section for hexagonal vertical Au NR arrays with a ~0.8 nm edge-to-edge gap distance along x-z plane and x-y plane. Transverse electric (TE) shows the polarization of a 785 nm
laser. (d) Volume maximum and average electric field EF as a function of the edge-to-edge gap distance. Copyright 2013, American Chemical Society.
Adapted with permission [93].

Fig. 8. Oblique view and close-up SEM images of periodically (a) Ag-capped Au nanopillar arrays and (b) bare Au nanopillars. The typical nanogap between neighboring
nanopillars is 10 nm and 50 nm, respectively. (c) Comparison of SERS spectra taken from the Ag-capped Au nanopillar arrays and bare Au nanopillars after exposure to 10−8 M R6G.
Copyright 2010, Wiley-VCH. (d) SEM images of core@shell nanoporous Au@Ag NR arrays, and structural illustration of the nanopores within each NR and the homogeneously
distributed gaps in the NRs. Copyright 2014, American Chemical Society. Schematic of multilayered (e) Au and (f) Ag NRs based on high-resolution nanotransfer printing. SERS
characterization results obtained from R6G-decorated respective nanostructures are also shown. Copyright 2016, Wiley-VCH.
(a-c) Adapted with permission [65]. (d) Adapted with permission [110]. (e-f) Adapted with permission [103].

and uniform structural nanoholes, such as a porous AAO template. Au nanopillar arrays then demonstrated outstanding SERS re­
This approach is easy to operate, cost-effective, and reproducible. producibility and EF (Fig. 8a–c). Similarly, MacFarlane et al. reported
More importantly, the size and neighboring gaps of the fabricated that by tuning the gap size between neighboring Cu nanorods into
vertically aligned metal nanorods can be easily tuned by changing the sub-10 nm regime through Ag or Au sputtering, the number of
the structural configurations of the template, such as pore ordering, hot spots was increased to significantly lower the SERS detection
pore size, length, and gap size [107]. However, the employed porous limit [108,109]. However, further coating of noble metals led to na­
AAO template is too fragile to use when its pore wall thickness is nogap blocking, thereby reducing the sensitivity of the SERS sub­
below 10 nm [108]. Therefore, many researchers have tried to opti­ strates.
mize and adjust the gap size of vertically aligned metal NRs to the Recently, in contrast to vertically aligned solid nanorods, 3D na­
sub-10 nm regime. The SERS sensitivity is greatly enhanced by re­ noporous SERS-active plasmonic metals have triggered tremendous
ducing the gap size between neighboring nanorods. For example, research interest owing to their large surface-to-volume ratio, ef­
Meng’s group found that sputtering Ag would shorten the inter- fective adsorbability of the target analyte, and high density of in­
nanopillar gaps of Au arrays to 10 nm [65]. The large area Ag-capped terior hot spots generated by the nanopores inside the porous

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

structure. Individual nanoporous Au NRs have shown clearly higher optoelectronic devices [112,113]. Recently, vertically aligned Si arrays
SERS sensitivity than that of the solid Au NRs [111]. Strikingly, are employed as versatile supporting SERS substrates due to their
Meng’s group presented large-scale, highly ordered core-shell high surface-to-volume ratio, which is useful in the creation of
Au@Ag nanorod arrays with nanopores by in situ dealloying and multiple hot spots. For example, Si nano or micro pillars (Fig. 9),
electrodeposition [110]. Both the nanopores in each of the nanorod nanohoodoos [114], nanocones [115], nanogrids [116], etc. The fab­
and the gaps between them lead to a homogeneous distribution of rication of uniform Si nano/micro-arrays with advanced character­
hot spots throughout the substrate (Fig. 8d). The as-fabricated arrays istics has been introduced in the Fabrication Methods section by
demonstrated sensitive and reproducible SERS performance for both using diverse technologies. Enhanced Raman signals of vertically
single- and dual-analytes, and show great potential in real-time aligned plasmonic Si nano/micro-arrays generally depend on the
detection. type, size, roughness, and shape of SERS-active metal nanoparticles
Vertically aligned metallic arrays in either solid or nanoporous (metal NPs), and especially on the distance or gaps between them.
form have shown superiority among various ordered plasmonic Various studies have focused on developing vertically aligned Si
metal nanostructures. Although plenty of aligned metallic SERS pillars with gap-rich plasmonic metals. Generally, the metal-deco­
substrates have been reported thus far, it is still desirable and rated vertically aligned Si pillars are classified into five types (Fig. 9a,
challenging to rationally design and fabricate highly ordered na­ 9c–f): metal NPs decorated on the sidewalls of Si pillars [27]; metal
nostructures with high density hot spots for further improved SERS capped on the top of Si pillars [45,50,117]; a combination of metal
performance. For example, Jeong et al. demonstrated the fabrication capping on the top and metal NPs-decorated on the sidewalls of Si
of vertically-stacked 3D cross-point plasmonic nanostructures over a pillars [118]; metal layers coated on whole Si pillars [30,31,119]; and
macroscopic area by high-resolution nTP (Fig. 8e–f), where high- metal NPs clustered on the top of Si pillars [26]. For example, Yang
density crossed points act as hot spots to achieve an enormous SERS and coworkers reported Au capped on hierarchically ordered arrays
signal [103]. More uniformly arranged 3D plasmonic metal nanos­ of noncircular Si nanopillars (Fig. 9d) where three Si nanopillars
tructures are expected in the coming future. were triangularly coordinated and the triangles were hexagonally
Highly ordered and well controlled metallic nanostructures have arranged [50]. The uniform Au-capped elliptical Si nanopillar arrays
shown superior SERS sensitivity and can even be used for SM de­ generated lateral couplings by utilizing the capped interparticle
tection. Nevertheless, their disadvantages such as difficulties in nanogaps, thus inducing highly intensified SERS signals with good
fabricating highly-uniform nanostructures at low cost have pre­ homogeneity. Lu and colleagues prepared Ag NPs clustering on the
vented wide applications. Therefore, several nanostructured non­ tops of hydrophobic Si nanopillar arrays by droplet-confined elec­
metallic substrates decorated with plasmonic metals such as troless deposition [26]. Therefore, the hot spots can be created ex­
metalized Si, ZnO, polymers, CNT, and graphene have been con­ clusively on top of the nanopillars (Fig. 9f) and are more accessible
sidered as alternatives. for the analyte molecules.
Besides the fabricated interparticle gap-abundant structure,
Silicon metal NPs deposited onto Si arrays, especially onto the sidewalls of
low-density Si pillars with a large pillar interspace, are other com­
Today, silicon is the most widely used semiconductor material. monly reported hybrid structures for SERS detection of chemical and
Due to its unique optical, electrical, and mechanical properties, biological analytes. However, the controlled deposition of active
various Si nanostructures are expected to be used for integrated nanoparticles onto such vertically aligned Si arrays still faces

Fig. 9. (a) Five types of metal distributions on vertically aligned Si arrays. SEM images of (b) Si nanopillar arrays and (c) 45° tilt view of Au capped on the thickened array.
Copyright 2016, American Chemical Society. (d) Hexagonally ordered and triangularly coordinated three Au-capped elliptical Si NW arrays. Copyright 2012, Wiley-VCH. (e) SEM
images of ~20 nm Ag film-coated Si NWs. Copyright 2013, American Chemical Society. (f) Ag NPs formed on the Si nanopillars. Copyright 2017, American Chemical Society. (g)
Hexagonal Si-micropillar arrays and (h) tree-like Ge-nanotaper/Si-micropillar arrays. Copyright 2015, Royal Chemical Society. (i) Ag micropillar arrays. Copyright 2017, Royal
Chemical Society. (j) Ordered Si/ZnO nanotrees. Copyright 2010, American Chemical Society. (k) Vertical array of Au nanostructures. Copyright 2012, Elsevier B.V.
(b-c) Adapted with permission [45]. (d) Adapted with permission [50]. (e) Adapted with permission [31]. (f) Adapted with permission [26]. (g-h) Adapted with permission [46]. (i)
Adapted with permission [39]. (j) Adapted with permission [75]. (k) Adapted with permission [120].

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

Fig. 10. (a) SEM image of Au NP-conjugated Si NR array (Au NPs = 20 nm) and (b) schematic under laser exposure. (c) FDTD simulation of the near-field intensity distribution at
633 nm of figure (a). Copyright 2017, American Chemical Society. (d) A sidewall SEM image of high-density hot spots generated by nanogap-rich Ag nanoislands (Ag NIs)
surrounding glass nanopillars and (e) the calculated electric field distribution near the hot spots. (f) Nanogap density between top nanoislands within the detection volume and
schematics of sidewall nanoislands within a 1 µm2 and SERS peak height (crystal violet 1 μ M) depending on the additive Ag thickness. The maximum SERS signals are shown with
a 30 nm thick Ag layer. Copyright 2012, Wiley-VCH.
(c) The polarization direction is set along the x-axis. (a-c) Adapted with permission [27]. (d-f) Adapted with permission [123].

challenges. The low diffusion of metal ions into the nanostructures Microarrays of Si pillars usually have large interspaces, which are
and unregulated aggregation of nanoparticles lead to nonuniformity very easily and frequently employed to fabricate hierarchical archi­
and area reduction of hot spots, as well as low reproducibility and tectures (Fig. 9g–k). Hierarchical Si-based structure arrays possess
difference of SERS signals, resulting in restriction of their practical expanded surface areas and structural complexity, which can load
use [27]. To overcome these problems and to attain spatial uni­ high density SERS-active metal NPs for the formation of hot spots.
formity of hybrid nanostructures, precise size and uniformity reg­ For example, Li and collaborators fabricated hydrophobic 3D bio­
ulation of noble metal NPs, for example Au NPs, on surfaces of Si mimetic Ag nanoplates on Si micropillar arrays (Fig. 9i) [39]. Fan and
arrays has been reported. Generally, the key step is the conjugation coworkers fabricated highly ordered Si/ZnO hierarchical nanos­
of Au NPs onto the surface of aligned Si arrays. For this purpose, Yang tructures [75], and decorated Ag NPs on them (Fig. 9j). Lee and
and coauthors utilized a “grafting onto” strategy, through which the colleagues reported Pt/CNT nets suspended on Si micropillars
Au NPs were uniformly decorated onto the surface of Si arrays (Fig. 9k), where Au was electrochemically deposited on this struc­
(Fig. 9a). In their study, 3-mercaptopropyltrimethoxysilane (MPTS) ture [120]. Kim et al. constructed a unique 3D “wire-on-pillar”
was used as a grafting material that can be easily eliminated by hierarchical architecture, in which Au nanowires (Au NWs) were
photolysis and has no interference with the Raman signal of the laterally grown from the sidewalls of Si pillars. The architecture
tested molecules [27]. On the other hand, large-area uniform de­ provides abundant hot spots between adjacent Au wires, which led
position of Ag nanoparticles (Ag NPs) onto Si vertical arrays through to remarkably high SERS intensity [47]. Meng’s group grafted Ge-
a polydopamine (PDA) coating approach was reported by Demirel nanotapers on hexagonally ordered Si micropillars (Fig. 9h), where
and colleagues [121]. They showed that in addition to serving as a Ag NPs were introduced via CVD. High density 3D hot spots were
reducing agent in Ag NP deposition, the PDA coating was also found generated from a large amount of adjacent Ag NPs, thus exhibiting
to contribute to SERS enhancement by promoting electron transfer strong and reproducible SERS activity [46].
and improving photon scattering processes with its organic semi­ On the other hand, low-density Si nanopillar arrays have distinct
conductor nature. The use of nanoparticles is not, however, limited advantages even though they cannot be hierarchically reconstructed.
to the “grafting onto” strategy. Lu and collaborators fabricated an Ag Si nanopillar array substrates relying on sub-10 nm electromagnetic
layer coating on Si nanowire (Si NW) arrays by employing 3-ami­ hot spots on either the top or sidewalls of pillars commonly suffer
nopropyltrimethoxysilane (APTMS) to avoid the Ag layer peeling off from weak reproducibility and stability of SERS signals, making it
from the Si nanostructures [122]. With these strategies, it is possible challenging to analyze long chain molecules (e.g., DNA, protein, and
to achieve spatial uniformity of metal NPs or strong metal coating polymeric species). To overcome this, plated Si nanoarrays with large
layers on the surface of the Si arrays, consequently ensuring interpillar spacing as SERS substrates have been reported, which is
homogeneous growth and leading to highly uniform and re­ quite suitable for uniform dispersion of analytes. Zhang’s group
producible SERS performance. fabricated Ag-coated hexagonal-packed Si nanopillar arrays as na­
In addition to the morphological and distributional properties of nogap-free substrates [29–31]. The controlled interspace and wide-
decorated plasmonic metals strongly regulating the density and range electric fields generated along the surfaces of Si pillars make
uniformity of hot spots, the distribution of Si pillars also has im­ this substrate suitable for label-free detection of long-chain double-
portant effects. Both dense and non-dense Si pillars can influence strand DNA, and an examination of this was also carried out by Yang
SERS hot spots in different ways. and coworkers [27]. Numerical simulations of an Au NPs-Si

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

nanopillar array showed that the areas around Au NPs are notably weak SERS activity of ZnO. Vertically aligned nanocone or nanorod
increased by LSPR. The simulation also revealed a horizontal zero- arrays (Fig. 11a, 11d–f) have distinguished ZnO architectures for SERS
gap field distribution between two Si nanopillars (Fig. 10a–c). applications, which can repeatedly scatter and trap the light. Most of
Unlike the low-density Si nanopillar arrays, high-density nano­ them are randomly oriented and can be typically grown by the seed-
pillar arrays, especially those with sidewalls decorated with metal mediated bottom-up method, as discussed in the Fabrication
NPs, can generate enough nanogaps between adjacent plasmonic Si Methods section.
or SiO2 pillars. In particular, Jeong and colleagues fabricated glass Vertically nanostructured ZnO arrays, as well as hierarchically
nanopillar arrays with nanogap-rich Ag nanoislands (Ag NIs) on the patterned ZnO nanostructures, could serve as frameworks for plas­
sidewalls of pillars, and Ag was formed as nanoislands owing to the monic metal anchoring and deposition (Fig. 11g–i). Therefore, ex­
growth in Volmer–Weber mode [123]. Through this strategy, cellent SERS activity of plasmon-active metal can crucially
the interstitial nanogap distance between Ag NIs on the top and side contribute to enhance Raman performance. A series of physical and
of glass nanopillars could be optimized by increasing the thickness chemical methods are available to deposit metal onto ZnO. In par­
of Ag (Fig. 10d–f), and thus generate strongly localized and high- ticular, site-specific deposition could be realized via electrophoresis
density hot spots to increase the SERS EF. Although these works [66], where suitable electrophoretic potential and sufficient growth
served as stepping stones in the research of nanogap behavior be­ duration create complete coverage on every ZnO NR (Fig. 11g).
tween adjacent plasmonic nanostructures, broader research is still Plasmonic metals are of great importance in elevating the SERS
needed to enable quantitative SERS at the SM level. activity of ZnO in hetero or hierarchical structures. However, the
SERS activity is influenced by parameters of both the vertical ZnO
Zinc oxide structure and decorated metals, such as ZnO shapes, ZnO sizes, and
the relative position between metals and ZnO. The distribution of
Semiconducting nanostructures are becoming one of the candi­ noble metals can be optimized during deposition, while the ZnO
dates for SERS substrates due to their distinctive features such as structures can be adjusted during growth. Several researchers have
low-cost preparation, controllable architectures, tunable photo­ tried to optimize parameters between ZnO structures and decorated
electric properties, and easy metallization capabilities [124]. ZnO is metals. Choi and collaborators designed finite element method
one of the simplest and most flexible semiconductors with a high (FEM) models containing elliptical Au heads on top of ZnO rods [72].
refractive index, on which nanostructures are able to develop into The smaller the interhead distance is, the greater the electron charge
various morphologies [125], showing great potential as active SERS oscillation will be. Additional Au deposition, however, resulted in a
substrates. decrease in the electric field because of the disappearance of the
Unlike plasmonic bandgap-free metals, the conduction band interhead gap. Huang et al. theoretically simulated EM field dis­
plasmon of semiconductors is generally in the infrared region while tributions of three structures with different distances: ZnO NRs and
the valence band is located in the UV region. Thus, LSPR cannot in­ single and neighboring Ag@ZnO structures [127]. Results showed
teract well with incident visible light, and the EM enhancement of that when two Ag@ZnO nanostructures were close to each other, the
semiconductors contributes weakly compared to that of noble me­ EM field was significantly strengthened. They consequently con­
tals [126]. As a consequence, numerous metalized ZnO nanos­ cluded that SERS hot spots located between neighboring Ag NPs
tructures were designed and produced to enhance the intrinsically were on both the individual and adjacent ZnO NRs. Moreover, Meng

Fig. 11. (a) Cross-sectional SEM image of ZnO nanowire (ZnO NW) arrays and (b) images of selectively grown ZnO NW arrays in different patterns. Copyright 2016, Royal Chemical
Society. (c) Photograph of the Au/ZnO NRs/graphite SERS-functionalized sensor. Copyright 2017, American Chemical Society. (d–f) Tilted SEM images of ZnO nanocones (ZnO NCs),
nanonails (ZnO NNs), and nanorods (ZnO NRs), respectively. (g) Ag-deposited ZnO NR array produced by electrophoretic deposition. Copyright 2015, Royal Chemical Society. SEM
image of ZnO NRs decorated with large Ag spheres on their (h) side surface and (i) upper surface. (j) Schematics of fabricated ZnO NRs arrays decorated with Ag NPs; there are
three kinds of “gaps” between the Ag NPs to form 3D hot spots, indicated as 1st, 2nd, and 3rd schematically. Copyright 2012, Wiley-VCH. (k) Ultrasharp ZnO NC arrays hybridized
with particle-on-film plasmonic systems. SEM images, the normalized electric field distribution, and 3D electric field contour plot are shown. Calculated field intensity of ZnO/Ag
NCs with and without Au NP along the height is given. Copyright 2015, American Chemical Society.
(a-b) Adapted with permission [71]. (c) Adapted with permission [72]. (g) Adapted with permission [66]. (h–j) Adapted with permission [69]. (d–f) and (k) were adapted with
permission [73].

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

and collaborators developed a very sensitive and uniform 3D hybrid colleagues presented a simple and reproducible method to fabricate
SERS substrate where, by controlling the sputtering condition, small a superhydrophilic SU-8 microstructured surface (Fig. 12d). Briefly,
Ag NPs and large Ag spheres were mounted simultaneously on the self-assembled SiO2 particles were embedded on a SU-8 surface and
side surface and on the top ends of vertically aligned cone-shaped subsequently removed by wet etching followed by plasma treat­
ZnO NRs, respectively (Fig. 11h–i) [69]. They critically classified the ment. Finally, Ag was deposited on the top of each nanopillar [135].
3D hot spots into three types (Fig. 11j): gaps between Ag NPs on the By controlling the embedding time of the SiO2 particles and plasma
lateral surface of the same NR, gaps between two Ag NPs on treatment parameters, two kinds of shape-controlled hexagonally
the lateral surface of two adjacent NRs, and gaps between two large ordered nanopillars were produced. After subsequent deposition of
Ag spheres on the tops of two adjacent NRs. Thus, the sensitive SERS Ag, triangular-shaped Ag nanoplates or monolayer of aggregated Ag
substrate possesses high-density hot spots in a 3D geometry. In NPs with nanoscale gaps were formed depending on the specific
addition, to achieve ultrasensitive SERS activity, Ko and collaborators structures. These SERS substrates showed high sensitivity and uni­
skillfully designed an Au particle – Ag film plasmonic ZnO NC array formity and provided a practical SERS-based sensing platform.
system for chemical sensors [73]. In this fabricated vertically aligned One of the advantages of polymer-based SERS substrates is that
heterostructure, the gap plasmons between Au NPs and Ag films the arrangement pattern and the geometry of vertically-standing
enhanced the SERS effect significantly in contrast with those of polymer posts can be varied with the mold used during nanoim­
interparticle surface plasmons (Fig. 11k). Furthermore, 3D conical printing. Both hexagonal and tetragonal arrays are therefore very
nanostructures with plasmonic particle−film system can allow im­ easy to obtain (Fig. 12e–g). The second advantage of polymer-based
proved light-trapping and waveguiding effects. This substrate can SERS substrates is the structural remodeling capability of primarily-
detect molecules (e.g., benzenethiol) at zeptomole level. formed polymer pillars, especially when using BCPs. The BCPs can
To allow the instantaneous in-situ detection and investigation of provide a template for producing nanostructures composed of con­
analytes, taper-like ZnO can be patterned inside a microfluidic tinuously connected pores through microphase separation, whereas
channel. Microfluidic-SERS platforms are favorable in many bio­ the imprinting technique uses cylindrical geometry for the local
chemical and biomedical applications [128]. In addition, to realize confinement of the BCPs. For example, Yang’s group used BCPs
detection and removal of analytes (e.g. Hg2+) and to subsequently confined in the microholes of an imprinting mold. After the mold
reuse the SERS active ZnO arrays, a photocatalytic self-cleaning ef­ was released, hierarchically structured SiO2 microcylinders with 3D
fect has been exploited for the removal of Hg2+ with the help of SERS nanopores were formed after reactive-ion etching (Fig. 12i–j) [67].
marker and UV exposure. The substrate can then be regenerated and Steinhart and collaborators used a similar pore formation method to
reused over many cycles [129]. Despite showing promising ad­ fabricate an array of porous nanorods having tips functionalized
vantages so far, vertically structured ZnO-based SERS substrates still with Au nanoparticles (Au NPs) (Fig. 12h). The nanopores were in­
suffer from some shortcomings including weak mechanical or che­ duced by selective swelling in warm ethanol for certain times [63].
mical stability and intrinsic defects that limit their use in real and Nanopores enable high loading of Au NPs and formation of abundant
broad applications [125], optimization and improvements of such hot spots, while vertical microcylinders structures facilitate the fast
issues are expected for further research. diffusion of analyte molecules through the nanopores, resulting in
significant enhancement of SERS intensity.
Polymers Another reason to choose polymers as SERS substrates is the
substrate-free standing property and flexibility. Compared to con­
Polymers have been one of the popularly used materials for SERS ventional SERS substrates, flexible 3D substrates can be in good
substrates due to their unique (e.g. elastomeric) properties for facile contact with complex surfaces, exhibiting superiority in sampling,
shaping into desirable morphologies with the aid of strategies such and rapid analysis with higher efficiency. Moreover, flexible sub­
as nanoimprinting and template-free patterning. Infusing coagulable strates can easily collect analyte molecules from real complex sur­
polymers into stamping molds via simple casting, or template-as­ faces via wiping or “paste and peeled-off” processes. Recently, a free-
sisted nanoimprinting, is the main method to prepare (vertically standing and flexible polydimethylsiloxane (PDMS) nanotentacle
aligned) polymeric pillars or tubes. Various distinctive polymer ar­ array was proposed by Han and coworkers (Fig. 12k). The platform
rays have been fabricated via this method, as has introduced in the can simultaneously detect three kinds of pesticides via a simple
Fabrication Methods section. “press and peeled-off” approach, showing practical SERS activity
Despite that nanoimprinting is still a generally used tool, tem­ [54]. Due to the flexibility of polymers, one of the most important
plate-free methods have also been reported to construct vertically reasons to use polymers is the easy self-coalescence capability of
aligned polymeric substrates (Fig. 12a–d). For example, Park et al. polymer pillars [57,59,130]. This will be discussed in the Capillary
and Kim et al. reported a simple, direct, and lithography-free process Force-driven Leaning Nanostructures section.
involving a smooth polyethylene terephthalate (PET) surface treated By applying diverse metal decoration approaches, various metal
with Ar plasma to form polymer nanopillars [130,131]. Choo and morphologies such as nanoplates and nanomushrooms not limited to
collaborators fabricated a 3D polyethylene naphthalate (PEN) plas­ the particle form can be regulated (Fig. 12e–g). While different from
monic substrate treated with O2 ion beams to generate a high areal nanoparticles or nanoplates decorated on polymeric pillar arrays, a
density of polymer nano-popcorn structure [132]. These maskless tunable but uniform metal layer coating on polymeric posts has also
etching processes can produce plasmonic nanopillar arrays posses­ been extensively investigated. ALD was adopted for conformal growth
sing high areal-density nanogaps over a several inch area after and for the reactive precursor gases to equally and easily reach the 3D
subsequent metal deposition. The facile process can even produce complex surface. Kang’s investigation showed that a moderate increase
flexible and circular hole arrays in large areas with the help of pat­ in the field enhancement can lead to a significant increase in the
terned shadow masks (Fig. 12a) [133]. In addition, Kang and collea­ predicted signal enhancement when the gap between two iridium-
gues fabricated a set of patterned dielectric skeleton pillar arrays coated nanopillars is small enough (Fig. 12l). They proved that the
into resists (hydrogen silsesquioxane, HSQ) with high aspect ratios enhancement with the iridium-based nanostructures is comparable to
by applying EBL [134]. Iridium-coated pillar arrays with high uni­ that of Ag-based reference substrates [134]. In short, polymer-based
formity can be further obtained after an atomic layer deposition vertically aligned SERS substrates have shown numerous advantages,
(ALD) coating process (Fig. 12b). Furthermore, in order to overcome but some weaknesses such as insufficient structural stability under
the poor wettability of Ag on a hydrophobic surface, Park and repeated laser irradiation require attention in future studies.

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

Fig. 12. Metalized PET arrays (a1) over a large area and its (a2) magnified SEM image. Copyright 2018, American Chemical Society. Fabricated hydrogen silsesquioxane (HSQ)
nanopillars (b1) before and (b2) after Iridium coating. (c) Polysiloxane/PS arrays coated with an Au layer. Copyright 2017, American Chemical Society. (d) Hexagonally ordered
triangular plate on top of each SU-8 pillar. Copyright 2013, American Chemical Society. The as-prepared (e1–i1) and metal functionalized arrays of (e2) hexagonal PAN, (f2)
tetragonal PAN, (g2) tetragonal NOA 61, (h2) porous PS-b-P2VP, and (i2) nanoporous SiO2. Copyright 2017, Royal Chemical Society, 2015 Wiley-VCH, 2016 Royal Chemical Society,
2017 Wiley-VCH, 2013 American Chemical Society, respectively. The nanoporous SiO2 array (i2) was derived from a PS-b-PDMS-b-PS triblock copolymer, as schematically illu­
strated in (j). (k) Schematic of PDMS array for SERS measurement. Copyright 2017, American Chemical Society. (l) Simulated distribution of the electric field, when the metal
thickness is increased and the gap width (g) is decreased. Copyright 2015, American Chemical Society.
(a) Adapted with permission [133]. (c) Adapted with permission [136]. (d) Adapted with permission [135]. (e-h) Adapted with permission [51,52,56,63], respectively (i) and (j)
were adapted with permission [67]. (k) Adapted with permission [54]. (b) and (l) were adapted with permission [134].

CNTs and graphene depending on the depth into the CNT array and the number of Au
NPs in each point along the CNTs can be seen in Fig. 13a. Femtomolar
CNTs and graphene are favored in SERS applications, and recently SERS sensitivity of a 4-mercaptophenol molecule was obtained by Au
there several approaches using CNTs and graphene to fabricate SERS NP aggregation followed by close positioning of these particles by
substrates have been reported [137–139]. Considering that light solvent drying and capillarity-driven nanotube agglomeration. The
collection and optical scattering occur in a 3D focal volume, a overall SERS intensity decreases with depth from the near top sur­
structurally tunable SERS substrate containing hot spots in a large face corresponding to the decline of the population of hot spots.
volume is highly preferred [77]. In pursuit of promoting the practicality of such substrates, another
VACNTs, which are constructed by bottom-up nonlithographic demonstration has been made by Park and collaborators. They reported
techniques, can provide an extremely dense and rough nanos­ a rational substrate design based on a metal-dielectric-CNT NW
tructure with densely decorated nanoparticles (e.g., Au NPs/Ag NPs). structure, which also demonstrated femtomolar-level detection sensi­
The diameters of vertical CNT nanowires (CNT NWs) vary from tivity of 1,2-bis(4-pyridyl)ethylene (BPE) by inserting a nanometer-
several nanometers to millimeters and were composed of a mixture thick layer of hafnia inserted between Au and CNT, and random
of double- and triple-walled nanotubes [77,140,141]. Recently, stacking of these Au-hafnia-CNT NWs [143]. The limitation of VACNT
Hafner and collaborators investigated the density of Au NPs along hybrids is generally large-scale preparation with high quality, and thus
the perpendicular axis of CNTs, where the VACNTs were synthesized the preparation and transfer of VACNT arrays from the growth surface
on a SiO2 substrate by water-assisted CVD, followed by Au sputter- to the target substrate is also important for VACNT based SERS sub­
coating (50 nm thickness) on top of the CNT array [77]. After a short strate fabrication. Furthermore, homogeneous assembly of SERS active
period of thermal annealing, different amounts of Au NPs form metal NPs on the VACNTs is also a continuous challenge.

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

Fig. 13. (a) Schematic and SEM images of Au NPs formed on vertically aligned CNTs along the perpendicular axis. Population of the Au NPs decrease from the top to the bottom of
the CNTs. The distance between each point(1–5) is 30 μm. All scale bars are 100 nm. Copyright 2012, Wiley-VCH. (b) Schematic and SEM images of the graphene-Au nano-pyramid
hybrid structure with energy level diagram of graphene–molecule interface and schematic of a R6G molecule lying parallel to graphene surface. Copyright 2013, Wiley-VCH.
(a) Adapted with permission [77]. (b) Adapted with permission [142].

On the other hand, combining the attractive features of graphene used Ag NPs has been shown to decrease in several weeks by more
and metal nanostructures or plasmonic metal incorporated di­ than 50% [161]. In contrast, the heterostructure based on graphene
electric nanostructures for SERS has garnered attention. As a single retains its sensitivity at nearly 100% for years [155]. Losurdo and
layer sp2-bonded carbon, graphene is characterized by its superior colleagues demonstrated and revealed the effectiveness of graphene
mechanical, thermal, chemical, and electrical properties [144]. It is as an electron shuttle to prevent and reduce oxidation of nanos­
now a versatile material in Raman spectroscopy owing to the fol­ tructured Ag/graphene hybrids, where Ag is kept in a metallic state
lowing reasons: 1) it is chemically inert and highly impermeable to for months under air exposure [149].
ambient O2 [145–147]; 2) it is transparent to a broad span of light As a new future of 3D scaffold and SERS substrates, CNTs and
and has the ability to suppress fluorescence, and thus can indirectly graphene are opening up new approaches and drawing enormous
enhance Raman signals [148]; 3) it can act as a protective layer to attention in recent years. Despite the remarkable progress made to
prevent the oxidation of metal nanostructures [149]; 4) it can be date, the extension of substrates, the improvement of the SERS en­
considered as an atomically thin spacer by placing it into nanos­ hancement by optimization of VACNT-metal nanostructures, and
tructured metals [150–152]; and 5) it shows good affinity to absorb graphene-vertical metal or other nanostructures are further re­
and concentrate various target molecules [142,153]. quired. In-depth theoretical and experimental investigations should
Recently, graphene-aligned metal nanostructures have received be exploited to understand the principles underlying the enhance­
much attention. The creation of graphene/metal hybrid nanos­ ment mechanism.
tructures is a classic method for the production of high-performance
SERS substrates combining EM enhancement and chemical en­ Biomaterials and biomimetic structures
hancement [142,154]. Xie’s group presented a highly active gra­
phene-Au hybrid platform consisting of a single layer graphene Numerous biological materials have been created through mil­
covering a quasiperiodic Au nano-pyramid array, demonstrating SM lion years of evolution. Many of the ordered natural architectures
sensitivity [142,155]. A single layer graphene superposed on an Au ranging in size from the macro- to nanoscale have drawn much at­
structure can not only locate SERS hot spots, but also change the tention in the field of SERS research. Vertically aligned sub-micro­
surface chemistry to selectively enhance Raman efficiency. They meter plasmonic structures found in natural materials have the
revealed the charge transfer property, stacking behavior, and vibra­ potential to further expand the arrangement of hot spots three-di­
tional coupling of molecules with graphene (Fig. 13b). Such a mensionally, which could increase the areal hot spot density.
structure realized nanomolar detection of target molecules. Another Furthermore, these 3D natural structures can guide the principles for
representative study of a graphene-aligned nanostructure hybrid design and engineering of bio-inspired artificial substrates with high
was carried out by Lu and coworkers: through modulation of hor­ SERS performance. Several kinds of vertically-shaped sub­
izontally patterned metal arrays, a graphene layer, and metal NPs, micrometer biostructures have been studied to date, such as wings
they established nanometer-scale gaps between metal NPs and of butterflies [162–166], cicadas, and dragonflies [167–169], taro or
metal arrays [150,156–158]. This type of metal NPs-graphene-metal lotus leaves [170]; rose petals [171,172]; diatom frustules [173], and
array exhibited high enhancement of the Raman response with a so on. Among them, butterfly and cicada wings have aroused con­
limit of detection to 0.1 × 10−12 mol L−1 along with good reliability siderable research interest.
and stability. One of the most complicated microstructures of the natural
Ag NPs and nanostructures are excellent plasmonic materials world is the butterfly wing [174]. A growing body of research has
with tunable LSPR from the visible to the NIR range, which are highly been performed on butterfly wings due to their excellent hier­
favored in SERS applications [159]. However, the primary drawback archical structures for SERS detection, especially the Morpho but­
of Ag based plasmonic materials is instability, where Ag is easily terfly family. The wing scale microstructures include so-called
oxidized into Ag oxide, showing LSPR red-shifts and dampening of “ridges” and “ribs” (Fig. 14a), where ridges are the most influential
optical resonances [149,155,160]. The Raman EF for the generally optical unit in scale as they are folded into overlapping lamellae

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

Fig. 14. (a) Morphology and structure of Morpho butterfly wing scales before and after coating different amounts of Au through PVD. (b) Schematic of vertical Au structures
templated by butterfly wings. From left to right: the original ridges and lamellae structures of the Morpho sulkowskyi butterfly wing; metallic NPs decorated at the surface;
conformal coating of a metal layer on the surface; 3D Au nanostrips on the top surface; minimization of the optical contribution from the template by immersing the butterfly
wing with 3D Au nanostrips in the RI matching fluid. Copyright 2018, Royal Chemical Society. (c) Rib-structures in Cu replicas converted from natural scales on different wing
positions of three kind of butterflies; stacking modes and numbers of ribs are marked herein. Scale bars: 500 nm. (d) Comparison of Raman intensities at 1650 cm−1 for R6G
molecules absorbed on different Cu scales. Copyright 2012, Wiley-VCH.
(a-b) Adapted with permission [162]. (c-d) Adapted with permission [163].

[162,165]. This kind of special structure offers a practical approach Numerous efforts have been dedicated to explore vertically
for complex 3D nanostructure fabrication that are difficult to achieve aligned and/or periodic metallic structures containing a high density
by traditional engineering techniques. The metallization approach of hot spots with the help of butterfly wings. Very recently, using
using Morpho butterfly wing templates can be classified into four particular wing scales from the Callophrys rubi butterfly as a soft
categories (Fig. 14b): (1) metallic NPs decorated on the surface of template, Zhang’s group reported a fabrication of gyroid-structured
wing scales; (2) conformally coated metal layer on the scale surface; Au SERS substrate with high density of 3D distributed hot spots. In
(3) 3D Au nanostrips deposited on the butterfly wing surface; and (4) this gyroid structure, the interconnected helices not only increase
immersion of Au nanostrips on butterfly wings in e.g., refractive the hot spot distribution in all three dimensions, but also help to
index (RI) matching fluid [162]. Among these categories, conformal increase the scattering cross-section of the incident laser [164]. The
replication of butterfly wing scales is the most frequently used Au deposition time was optimized to obtain ultra-high SPR sensi­
method to construct metallic structures with well controlled hier­ tivity as well as reproducibility and uniformity (Fig. 15a–c).
archical morphologies. This process generally involves three proce­ The cicada wing is another biomaterial possessing unique and
dures: pretreatment of wing scales, metallization, and removal of brilliant microstructures in the natural world. Unlike butterfly
the original scaffold. Zhang and collaborators conformally replicated wings, cicada wings have ordered arrays of nanopillar structures. The
3D sub-micrometer structures of butterfly wing scales into Ag with chitin nanopillar arrays show a new bioscaffold for decoration with
high structural periodicity through a simple room-temperature metal NPs of different dimensions to realize an ordered SERS sub­
photoreduction process [175]. Gu and his colleagues have proposed a strate. The metallization process is relatively simple compared to
specific process for a functional surface and a subsequent procedure that of butterfly wings, generally by a straightforward deposition
of electrical deposition to produce metallic (Ag, Au, Co, Cu, Ni, Pd, method. Thus, the fine control of metal gap sizes has been the main
and Pt) replicas of the intact 3D butterfly wing scales [165]. Fur­ focus. Both Au and Ag NPs deposited on cicada wings have been
thermore, they reported Cu structures with optimal conformal reported so far. Through thickness control of the Au film deposited
morphologies replicated from butterfly wing scales through opti­ onto the cicada wing, Qian and collaborators studied the effect of
mizing Cu deposition conditions [163]. “Rib-structures” with a gap sizes between neighboring nanopillars [169]. Furthermore,
20–30 nm period on the sidewalls of the “main ridges” of the wing Han’s group has elaborately developed and managed hierarchical
scales play a crucial role in piling hot spots arranged along the “Z” nanogaps on the chitin nanopillar arrays with Ag NIs on the side
direction perpendicular to the scale (Fig. 14c–d). Other than con­ surfaces and Ag nanoflowers (Ag NFs) on the top ends [168]. The Ag-
formal coating, metallic NP decoration on the wing scale surface is decorated chitin nanopillars have four types of nanogaps, creating
another commonly used method. Zhao and collaborators in situ 3D hot spots in a high density (~2000 µm−2) (Fig. 15d–e): nanogaps
synthesized Au NPs on a butterfly wing [176], while Zhang and between the Ag NIs located on the lateral surfaces of single chitin
collaborators synthesized Ag NPs/graphene composites; in both nanopillar (type I); nanogaps between the Ag NIs located on the
cases the graphene acted as a protective layer for long-term stability lateral surfaces of neighboring chitin nanopillars (type II); nanogaps
improvement of their arrays even after six months [177]. within the Ag NFs located on the top ends of neighboring chitin

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

Fig. 15. (a) Schematic of the gyroid-structured Au periodic metallic material (left) and relative positions of the four energy maps labeled on the gyroid model with one unit cell
(right). (b) Exponential distributions of the calculated electric field enhancements on the [100] plane directions with different z depth at a volume fraction of 75% based on the
gyroid model. The inset shows the TEM projections with corresponding z depths in the [100] direction. (c) Variation trends of the crystal violet (CV) peak SERS signal intensities at
wavenumber 1617 cm−1 versus td detected from two zones in the butterfly wing scales. (d) Illustration of Ag-decorated chitin nanopillar arrays. Through sputtering, Ag nanoislands
and Ag nanoflowers are formed simultaneously on the side surfaces and top ends of chitin nanopillars with hierarchical nanogaps, respectively. (e) FDTD simulations showing the
electric-field distribution of (d). Copyright 2013, American Chemical Society.
(d) Adapted with permission [168].

nanopillar (type III); nanogaps between the Ag NFs located on the periodicities by phase-shift IL on sub-micrometer length scales
top ends of the single chitin nanopillars (type IV). [41,182]. A standing wave could be generated by a strongly re­
The current challenge to obtain a high density of nanogaps and flecting incident laser beam at the boundary between the photo­
uniform spatial distribution of SERS intensity can be partly solved resist film and underlying substrate. Every nanopillar was
using the natural templates that consist of repeated nanogaps in a sculpted as a disk-stacking structure with 20 nm-thick nanogaps
vertical direction. However, natural templates may not be avail­ using this standing wave (Fig. 16c, 16f). The vertically integrated
able for mass production [178], and in the case of direct replica­ metal nanogaps enabled strong EM field localization and thus
tion of natural templates, it is still difficult to fully control the effectively enhanced Raman signals. The pagoda-like nanoarchi­
geometrical features of nanostructures. Therefore, the design and tecture arrays can be regularly arranged over a wide area of 1 cm2
fabrication of biomimetic materials has been brought into focus and promote the wetting of sample fluids without spreading. To
recently. Many of the complex bio-inspired architectures, such as optimize the SERS activity of the special architecture, they regu­
lotus leaf-like [179], lotus seedpod-like [180], and sunflower-like lated the nanopillars by growing stories and tapering the nano­
[181] nanoarrays have been studied. In particular, Kim and colla­ pillars into a cone shape. Comparison and simulation have shown
borators elaborately fabricated butterfly scale-inspired, pagoda- that the tapered nanopillars with eight stories has the highest
like nanopillar arrays (Fig. 16a–b, 16d–e) with three distinct SERS activity (Fig. 16g).

Fig. 16. (a) SEM images of nanopillar arrays with undulating side walls. Si is used as a substrate. A side view of a single nanopillar is shown in the inset. (b–c) A set of SEM images
of Ag-deposited cylindrical nanopillars with eight stories and a section of the FDTD calculation corresponding to the structure. (d) Low and (e) high- magnification SEM image and
(f) FDTD calculation of the cone-shaped nanopillars with eight stories. Diffraction colors from the nanopillar array are shown in (d) inset. (g) Spatial distribution of the electric
field intensity and integrated values along the surfaces of the three different nanopillar structures, which are normalized with respect to that calculated from the cone-shape ones
(left y-axis); the experimentally estimated Raman EF for the three structures (right y-axis). Copyright 2015, Wiley-VCH. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
Adapted with permission [41].

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

Structure engineering and probe sensing strategies towards deposition and etching techniques is the most commonly used ap­
ultrasensitive detection proach because this top-down method can produce more uniform
and reproducible nanostructures with high controllability, which
Uniquely designed nanostructures would provide SERS signals that are comparatively uniform and re­
producible.
To detect probe molecules at ultralow concentrations even down Various multi-branched nanostructures with distinct character­
to the SM level, ideal SERS substrates should meet significant cri­ istics have been reported to date. For example, Gu and collaborators
teria, including a sufficiently high EF, uniformity, reproducibility, and showed vertically aligned Au bowtie nanoantenna arrays (Fig. 17a)
a facile fabrication method [27,50,58,183,184]. Thus far, several sys­ with optimized periodicity [187,188]. It is noteworthy that the en­
tematic studies have revealed that extremely small amounts of hancement can be significantly improved by increasing the dimer
analyte molecules adsorbed at the hot spot with strong EM fields structures from the ground to a 3D geometry, resulting in large SERS
contribute a huge amount to the overall SERS signal [185,186]. EFs exceeding 1011; Choi and collaborators fabricated 3D metallic
Therefore, in the last few years, increasing focus has been paid to structures consisting of multiple petals with a uniform and re­
creating unique nanostructures that have sufficient sub-10 nm gaps producible shape (Fig. 17b) using a spark discharge and ion-induced
and very large near-field confinement, as well as positioning probe electrostatic focusing method [183]. Both the numbers and field
molecules into these gaps. To this end, nanostructures arranged in intensity of hot spots formed at the nanogaps located between ad­
various forms such as dimers, arrays or clusters with sub-10 nm gaps jacent petals were increased with an increasing number of petals.
have been broadly reported for hot spot engineering. But they often Very recently, Chirumamilla and colleagues fabricated nanostar-
suffer from irreproducibility and a lack of uniformity owing to shaped arrays with different numbers of arms elevated from di­
practical limitations [184]. Alternatively, unique plasmonic nanos­ electric substrates to avoid hot spot trapping in the bulk substrate
tructures containing multiple branches and definite sharp protru­ [184]. This study elucidated the effect of the branch numbers on hot
sions that are periodically aligned over a large scale are therefore spots (Fig. 17d). They confirmed that, for planar substrates, the local
ideal candidates. These multi-branched nanostructures, demon­ near-fields are confined at the interface between the metal and the
strated in shapes such as bowties (Fig. 17a) [187–189], flowers underlying dielectric material, weakening the near field enhance­
(Fig. 17b–c) [99,183], and stars (Fig. 17d–f) [184,190–192], represent ment and limiting the accessible regions for molecule detection.
an excellent geometry due to the existence of multiple sharp tips or However, elevated 3D geometries have multiple advantages com­
corners, which can efficiently provide strong localization of electric pared to conventional 2D planar structures: the enhancement of the
fields. In this section, we especially introduce such unique ordered plasmonic field is stronger because it is effectively decoupled from
nanostructures bearing spatial hot spots in the vertical direction. the underlying substrate with the aid of the dielectric nanopedestal;
Multi-branched nanostructures can be realized by various the regions of enhanced local EM fields are then more accessible to
methods, but electron or ion beam lithography combined with metal the probe molecules. Furthermore, to statistically ensure that there

Fig. 17. (a) Elevated Au bowties on top of Si posts with a gap of 8 ± 1 nm. Copyright 2010, American Chemical Society. (b) 8-petal flower arrays with etched pattern geometries.
Copyright 2014, Wiley-VCH. (c) Flower-like structure arrays. Copyright 2011, American Chemical Society. (d) Branched nanostructures with 3D perforated metal topology. The
branch effect on electric field distribution and SERS performance, topology effect, and laser excitation wavelengths were also investigated. Copyright 2017, Wiley-VCH. (e)
Nanostar dimers on Si pillars. The interparticle spacing and pillar height effect on the SERS intensity were investigated. Raman spectrum recorded from adenine chemisorbed from
1 pM concentration is shown. Copyright 2014, Wiley-VCH. (f) AgAu bimetallic vertical nanostar dimer in a ring structure. The respective electric field distribution in the x-y plane
of a single AuAu and AgAu nanostar dimer, and a AgAu nanostar dimer in a ring was evaluated. Pillar height effect on SERS intensity of the peak at 1077 cm−1 of pATP (10 μ M)
molecules, and SERS spectra recorded from adenine molecules with concentrations of 1 μ M, 1 n M, and 1 p M were recorded, respectively. Copyright 2014, American Chemical
Society.
(a) Adapted with permission [188]. (b) Adapted with permission [183]. (c) Adapted with permission [99]. (d) Adapted with permission [184]. (e) Adapted with permission [190]. (f)
Adapted with permission [191].

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

is only one or a few molecules per hot spot, they introduced complex low surface energy. 3D constructed architectures, especially
3D star-shaped metallic (Au) dimer arrays with uniform and re­ micro/nanostructures aligned in the vertical direction (Fig. 18a), have
producible sub-10 nm tip-to-tip gaps over large area, the arrays can been proven to be ideal candidates for obtaining a hydrophobic
be used to detect various biomolecules at very low concentrations surface [39,42]. When a droplet of an extremely diluted solution is
(~1 pM) (Fig. 17e) [190]. More importantly, they upgraded this na­ dropped onto a hydrophobic structural surface, the droplet will
nostructure into a circular ring, which was achieved by depositing maintain a spherical shape, with its solute being concentrated
bimetallic AgAu layers onto the nanostructure [191]. Circular rings during solvent evaporation (Fig. 18b). This hydrophobic con­
incorporated into this nanostructure act as reflectors and can create centrating effect can allow trace-amount detection of analytes by the
a diffractive coupling that reflects the light back to the center of the SERS technique [39,40,42,196].
ring where the dimer arrays are placed, thereby enhancing the local Typically, there are three methods to obtain vertically aligned
EM fields at this center (Fig. 17f) [193,194]. This 3D-nanostar-dimer- micro/nanostructures with sufficient hydrophobicity: direct use of
in-ring structures can even be recycled by maskless metal etching natural architectures [170,172], biomimetic fabrication of vertically
and deposition. aligned micro/nanostructures [39,59], and hydrophobization of the
In brief, these uniquely designed SERS substrates open the way surface of general 3D structures [26,40,42,130,196]. It is well known
for practical application through scalable production of ultra­ that natural species possess hydrophobicity owing to their complex
sensitive SERS devices. The unique properties offered by multi- but spatially elaborate structures, such as the surface of a lotus leaf
branched architectures hold promise for the development a new era or a rose petal, which can be exploited for analyte enrichment and
of potential commercialization sensing technology. therefore improve the SERS detection limit [170,172]. Subsequently,
these natural materials have aroused great interest to develop new
Surface-energy engineering types of hydrophobic biomimetic materials, either with or without
surface energy reduction by fluorinated reagents. Several artificial
The design and fabrication of unique nanostructures, as men­ hydrophobic SERS substrates have been developed to date. Lu and
tioned above, has proven to be a highly effective way to achieve coworkers demonstrated an efficient modification of Si nanopillar
ultrasensitive and reproducible SERS analysis. Nonetheless, posi­ arrays with fluoroalkylsilane, which benefited the subsequent me­
tioning as many probe molecules as possible into electromagnetic tallization process and contributed to the concentration of molecules
hot spots with nanometer precision, namely concentrating or en­ on the top of the pillars [26]. Li and collaborators fabricated hy­
riching analytes, is another requirement for SERS-based ultra­ drophobic 3D biomimetic Ag nanoplates on Si micropillar arrays for
sensitive detection in recent years. It tends to be difficult to enrich ultrasensitive and reproducible detection of explosives (Fig. 18c)
and deliver the analytes to a specific SERS detective area when [39]. More importantly, Park and colleagues showed an example of
considering controllability and reproducibility. In this section, we surface energy-controlled SERS substrates for concentrating mole­
introduce surface energy-controlled vertically aligned 3D nanos­ cules in their research [130]. The surface energy of the plasmonic
tructures and their performance towards ultrasensitive and re­ nanopillar arrays was precisely controlled through the selective re­
producible SERS detection through analyte concentration. moval of the low surface energy molecule layer, providing a rea­
Wettability is a significant property of a nanostructured surface sonable hydrophobic surface ready for use. Distinct evaporation
that is highly dependent on its “surface energy”. The surface energy behaviors from their plasmonic nanopillar arrays were observed for
can be precisely tuned through various strategies [195], such as different surface energies (Fig. 18e).
controlling the surface topography or attaching low surface energy The hydrophobic effect has shown great versatility when in­
molecules, which generate a hydrophobic surface with reasonably tegrated on SERS substrates for ultrasensitive detection. However, it

Fig. 18. (a1) Periodical Si microarrays and (a2) the top of a single pillar decorated with Ag NPs via electroless deposition. (b1) Solute precipitation from a 1 fM solution of
rhodamine and (b2) its fluorescence measurements. Copyright 2011, Macmillan Publishers Limited. (c) Recorded images of the evaporation process on the surface of vertical
biomimetic superhydrophobic Ag micro-pillar arrays. Copyright 2017, Royal Chemical Society. (d) CAs of five different liquid drops on the stacked-disk nanotower arrays. (e) Time-
dependent variations of the water CA on plasmonic nanopillar arrays with different wetting conditions. Copyright 2017, Wiley-VCH. (f) Apparent CAs (θA) of five different liquids
on the stacked-disk nanotower array (squares) or nanocylinder array (circles) as a function of the equilibrium CAs (θE). Copyright 2016, Wiley-VCH.
(a-b) Adapted with permission [40]. (c) Adapted with permission [39]. (e) Adapted with permission [130]. (d) and (f) were adapted with permission [42].

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

has been shown that such sensitive detection is highly related to the hot spot aggregations and to trap target molecules into such a po­
size of the final area after the analyte solution droplet has evapo­ sition favorable for practical plasmonic sensing applications. In this
rated [179,197]. Therefore, superhydrophobic textured surfaces section, we discuss the leaning nanostructures designed for SERS
should meet the requirements of having a large contact angle (CA) analysis, including the driving force of leaning, structural effects,
(> 150°) and an ultralow adhesive feature in order to effectively molecule trapping mechanism, and key factors toward practical
enhance the SERS intensity by concentrating analyte molecules. applications such as recyclability.
Ultralow adhesion force between the droplet and the surface allows The leaning behavior of vertically aligned nanostructures could
the droplet to slide on the surface during evaporation, thereby be explained by the drying-driven capillarity effects in most cases,
avoiding being pinned at its initial contact point. Finally, the analytes which can be specifically explained as follows. A droplet of the sol­
are trapped with high concentration in a small area where the hot vent (e.g., water) is first placed onto the nanostructured substrate
spots are mainly located. Through this approach, the detection of followed by drying/evaporation of the solvent. When the capillary
only a few molecules is possible. Fabrizio et al. reported nano­ force and/or the adhesion force between the pillars is greater than
plasmonic vertically aligned Si structures covered with Ag nanograin the restoring elastic force, neighboring pillars will lean toward their
aggregates (Fig. 18a–b), which were superhydrophobic with high CAs nearest neighbors, forming bundled micro-scale clusters and thus
and low friction forces (low friction coefficient) after fluorination creating a large number of electromagnetic hot spots (sub-nan­
[40]. By driving highly diluted solutions into a very small region (a ometer gap junctions) where the target analytes are trapped. For
few tens of micrometers), their substrates allowed SM detection at example, Meng and collaborators fabricated an ordered array of Ag
femto- or attomolar (10−15/10−18 mol L−1) levels. nanorod bundles that were vertically grown on a large-area Au/Cu
Superhydrophobic structures, however, are limited in use be­ substrate in the shape of a hexagonal lattice [198]. During the ca­
cause they are only effective for analytes dissolved in water. Because pillary force-induced leaning process, a small gap (≈ 2.1 nm) was
most organic molecules have low solubility in aqueous solutions and formed between every two adjacent nanorods at the top end. Each of
weak absorption to substrates, omniphobic structural surfaces have the optimized Ag NR bundles consists of 30–45 leaning Ag NRs.
received substantial attention recently. Superomniphobic SERS Theoretical calculation revealed that the highest EM field enhance­
substrates refer to surfaces with antiwetting properties toward ment was achieved at a gap of 2 nm among several simulated se­
various solvents, including water and other solvents, which typically paration distances (Fig. 19h). Although the driving force of the
comprise hierarchical micro- and nanoscale structures grafted with leaning effect in most reported works is capillarity force, there is
omniphobic functionalities. Ling and coworkers fabricated a super­ another driving force involved in the phenomenon. Xu and cow­
omniphobic SERS platform by vertically stacking Ag nanowire orkers reported an ordered, hierarchically structural Ag-decorated
(Ag NW) mesh-like arrays that were able to repel various common PMMA nanorod array, where seven nanorods in one unit bend due to
liquids after fluorination including water, ethylene glycol, dimethyl a plasmonic heating effect and their metal-decorated tops assemble
sulfoxide, toluene, and n-dimethylformamide [196]. On the other collectively [59]. FDTD results show that in the aggregated state,
hand, Kim and collaborators elaborately designed stacked-disk na­ there is a strong local field coupling at the sub-10 nm gap between
notower arrays with an Ag outer coating as omniphobic SERS sub­ the tops of the contracted nanorods, which is higher than that of the
strates [42]. The stackeddisk nanostructures provided strong electric separation state. Compared with wetting and drying assisted struc­
field localization at the vertically integrated nanogaps in each tower- tural leaning, using light as an external stimulus is much more facile
like post (Fig. 18d). Furthermore, the reentrant geometry of the na­ and tunable at the nanoscale.
notower walls efficiently supported the liquid and created a liqui­ Randomly oriented nanostructures can also approach each other
d–air interface for a variety of liquids after chemical modification closely to form leaning structures. In fact, the aspect ratio of the
with fluorothiols. Apparent CAs (θA) of five different liquids on the nanopillars or nanowires of this kind is a crucial factor to initiate the
stacked-disk nanotower array (squares) or nanocylinder array (cir­ leaning phenomenon. A general concern for the fabrication of this
cles) as a function of the equilibrium CAs (θE) were studied, in­ type of substrate is that the aspect ratio of the pillars should be
dicating superiority of the nanotower geometry compared to sufficiently high that the nanostructures are flexible enough to un­
nanocylinder structure (Fig. 18f). dergo a self-closing process towards their nearest neighbors even
Vertically structured SERS-active substrates with super­ when subjected to relatively weak forces. Schmidt and colleagues
hydrophobic or omniphobic properties have been proven to be evaluated the leaning performance of disordered Si nanopillars with
highly effective towards reproducible and ultrasensitive detection. heights between 600 nm and 1600 nm where their height depended
However, few studies have been reported to date, and alternative linearly on the maskless dry etching time [202]. Liu and collabora­
nanostructures with high CA and low CA hysteresis or omniphobic tors confirmed that long nanorod arrays (height ~1 µm) can re­
properties are expected to be further exploited for more practical versibly self-close while short nanorod arrays (height ~200 nm)
SERS applications. cannot [205]. Park and colleagues showed hybrid Au/PET nanopillars
with an aspect ratio of 3 clustered together through capillary leaning
Capillary force-driven leaning nanostructures effects [130]. In addition, in some cases the leaned pillar amount
could influence the SERS enhancement. For example, Li and cow­
Recently, leaning of metal NRs, metallized dielectric nanowires, orkers elaborately assembled finger closing-like polygons, which
nanopillars, and nanofingers has been shown to be critical for gen­ were formed on top of predefined flexible polymer pillars that un­
erating exceptional EM field enhancement for SERS applications. Hot dergo self-coalescence. It was found that the symmetry of the
spot aggregates with sub-5 nm gap sizes can be formed by control­ polygons determined the number and strength of potential plas­
ling the geometry of vertically aligned nanostructures, and analytes monic hot spots between adjacent Au NPs [57].
can be trapped at the junction in a “metal-molecule-metal” form The trapping mechanism of target analytes during the leaning
under incident laser illumination [57]. So far, the leaning phenom­ process was also investigated by several researchers. It is generally
enon of various metals or metallized dielectric nanostructures has regarded that post-leaned pillar/wire configurations showed greater
been reported for either ordered or disordered structural morphol­ SERS EF enhancement compared to pre-leaned and non-leaning
ogies (Fig. 19a-g), including Ag NRs [198], Ag nanotube arrays [80], pillar/wire configurations. This indicates that some potential hot
Au or Ag-decorated polymer nanofingers [57,199,200], Si nanopillars spots or adsorption sites are negated by leaning prior to analyte
[28,37,130,201,202], and ZnO NWs [128,203]. To date, it is still an exposure (Fig. 19i), which has been confirmed by Giovannozzi and
intriguing challenge to create leaning structures with controllable Schmidt’s research [28,202]. On the other hand, chemically trapped

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Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

Fig. 19. (a) Self-closed Au fingers. (b) Pentagon-shaped closed nanofinger assemblies. Copyright 2011, American Chemical Society. (c) As-prepared Ag NR bundle arrays. (d)
Ag-coated clustered ZnO NRs. Copyright 2011, Royal Chemical Society. (e) Clustered Au/PET nanopillar array with an aspect ratio of 4. (f) Molecular enrichment at the plasmonic
nanogaps on top of the nanopillars through (f) continuous nanopores, or (g) precise control over the surface energy. Copyright 2017, Wiley-VCH. (h) The measured gaps between
the neighboring Ag NRs and distribution and FDTD simulation. Copyright 2016, Wiley-VCH. (i) Raman spectra comparison of leaning and non-leaning Si nanopillars. Copyright
2012, Wiley-VCH. (j) Schematic of the preparation of preclosed and BPE-trapped Au fingers. (k) N 1s high-resolution X-ray photoelectron spectroscopy (XPS) of BPE multilayer
sample, preclosed fingers, and BPE-trapped fingers (N1, free nitrogen; N2, weakly adsorbed nitrogen; N3, bridged or strongly adsorbed nitrogen). Copyright 2011, American
Chemical Society. (l) TNT-induced resonance Raman enhancement of PABT on the top-closed Ag nanotube array. Copyright 2011, American Chemical Society. (m) Workflow of
recycling the alumina/Si nanohoodoos. Copyright 2017, Wiley-VCH.
(b) Adapted with permission [57]. (d) Adapted with permission [203]. (e) and (g) were adapted with permission [130]. (f) Adapted with permission [63]. (c) and (h) were adapted
with permission [198]. (i) Adapted with permission [202]. (a) and (j–k) were adapted with permission [199]. (l) Adapted with permission [80]. (m) Adapted with permission [204].

molecules inside the leaned tips was investigated by Li and cow­ self-approaching of flexible Ag nanotubes driven by the capillary
orkers. They employed BPE molecules as trapped molecules [199]. force of solvent evaporation can spontaneously form Raman hot
The binding behavior of BPE on flexible Au nanofinger arrays was spots in a reversible manner (Fig. 19l) [80]. Very recently, Boisen and
studied by SERS and angle-resolved XPS (Fig. 19j–k). The results in­ collaborators designed and fabricated prepatterned alumina/Si
dicate that BPE molecules are trapped between the finger tips in a nanohoodoos (Fig. 19m), on which Au NPs can slide and aggregate
bridging configuration through the lone pair electrons of the pyridyl into particle clusters with strong, dense, and uniform EM hot spots
nitrogen from BPE. when a deposited analyte solution is dried [204]. This substrate can
While probe molecules dissolved in liquid may become trapped be recycled upon fully eliminating the Au nanostructures via a wet
among the nanogaps at the top of the nanopillar clusters, solution etching step and renewed by remetallization for each next SERS
drops can possibly penetrate to the basis of the nanopillars. analysis, maintaining identical SERS performance even after eight
Therefore, Steinhart and collaborators fabricated an array of porous iterations of recycling.
nanorods. The special structure facilitated fast diffusion of analyte
molecules from the tips to the bottom surface through the nano­
pores (Fig. 19f) [63]. Park et al. attempted to control the surface Potential applications
energy of the plasmonic nanostructures to improve the analyte
concentration at the clustered tips (Fig. 19g). These approaches en­ Vertically aligned nanostructures are desirable for SERS appli­
able practical SERS-based sensing applications from a distinctive cations due to various characteristics including strong SERS en­
perspective [130]. hancement from increased density of hot spots, increased surface
Ideally, hot spots for practical chemosensing purposes should area, and fine control along the Z-axis to tune output conditions.
also be reversible and renewable. Researchers have shown progress Such unprecedented SERS enhancement levels from vertically
in this regard [80,204,205]. Wang and collaborators showed that the aligned nanostructures make SERS applicable to various fields such

20
 Table 1
Summary of various vertically aligned SERS-active nanostructures.

Type of Morphological & geometrical features Fabrication approach Hot spots types Advantages Potential weaknesses
nanostructure
Y. Liu, M. Kim, S.H. Cho et al.

Metals arrays of nanorod, nanopillar, nanowire or self-assembly nanoimprinting; sharp tips, corners, and inter-gaps superior SERS sensitivity fabrication cost
nanorod bundles; nanoporous; mixed electrodeposition; nano-transfer between nanorods, pillars, and
metals; multi-stacked printing nanopores
Silicon-based Substrate: hexagonal or tetragonal arrays photolithography; nanosphere Gaps between metal nanoparticles on Diverse fabrication methods; high low diffusion of metal ions into the
of nano or micro pillar; Bowtie, flower or lithography; metal-assisted chemical sidewalls; Gaps between metal surface-to-volume ratio; easy to nanostructures; unregulated
star arrays; nanoplate or nanotree on etching; deep reactive ion etching; e- nanoparticles on the top of pillars; Gaps fabricate hierarchical architectures aggregation of nanoparticles
micropillar arrays; wire-on-pillar arrays beam lithography between metal layers on adjacent pillars; for micropillars
Plasmonic Metal: on sidewalls of pillars; Gaps from adjacent nanoparticles on
capped or clustered on the top of pillars; hierarchical architectures
layer-coated on whole pillars
Zinc oxide-based Substrate: randomly oriented arrays of thermal decomposition of precursor; gaps between Ag nanoparticles on the easily integrated into SERS active weak mechanical or chemical stability;
nanowire, nanocone, nanonail or nanorod seed-mediated physical deposition; lateral surface of the same nanorod; gaps platforms, e.g., microfluidic-SERS intrinsic defects
Plasmonic Metal: on the lateral surface; screen-printing; hydrothermal between two Ag nanoparticles on the platform; potential photocatalytic
as head on top of rods method lateral surface of two adjacent nanorods; self-cleaning effect
gaps between two large Ag spheres on
the tops of two adjacent nanorods
Polymers-based Substrate: hexagonal or tetragonal arrays nanoimprint lithography; maskless gaps between triangular-shaped Ag polymer posts can be varied with insufficient structural stability
nanopillar or nanopost; finger-closing etching with Ar plasma or O2 ion nanoplates or aggregated Ag the mold used; structural
pillar arrays; nanoporous beams; e-beam lithography nanoparticles; gap between two metal- remodeling capability; substrate-
Plasmonic Metal: nanoparticles; metal coated nanopillars; free standing property and
layers; nanoplates or nanomushrooms on flexibility

21
top of polymer pillars
CNTs-based Substrate: vertically aligned nanowires seed-assisted chemical vapor gaps between metal nanoparticles, the extremely dense and rough large-scale preparation with high
along the perpendicular axis deposition population of hot spots decrease with nanostructure quality; CNTs transferable performance
depth from the near top surface after growth; Homogeneous assembly
of metal nanoparticles on the CNTs
Graphene- graphene-vertical metals or other – – chemically inert; low fluorescence; more investigations needed to
assisted nanostructure hybrids prevention of metal oxidation; understand the principles underlying
used as a spacer between metals; the enhancement mechanism
good affinity to target molecules
Biomaterials- Substrate: wings of butterflies, cicadas, – For Ag on cicada wing: gaps between the natural structures; diversity may not be available for mass
assisted dragonflies; taro or lotus leaves; rose Ag nanoislands on the lateral surfaces of production; difficult to fully control the
petals; diatom frustules single chitin nanopillar; gaps between geometrical features of
Plasmonic Metal for butterfly wing: on the Ag nanoislands on the lateral nanostructures
the surface of wing scales; conformal surfaces of neighboring chitin
layer on the scale surface; nanostrips on nanopillars; gaps within the Ag
the wing surface; gyroid-structured nanoflowers on the top ends of
neighboring chitin nanopillar; gaps
between the Ag nanoflowers on the top
ends of the single chitin nanopillars.
Biomimetic- Substrate: lotus leaf-like; lotus seedpod- nanosphere lithography; phase-shift metal layers as a disk-stacking structure nanopillars can be regulated by complicated fabrication
based like; sunflower-like; butterfly scale- interference lithography with 20 nm-thick nanogaps growing stories in case of pagoda-
inspired, pagoda-like like nanostructure
Nano Today 37 (2021) 101063
Y. Liu, M. Kim, S.H. Cho et al. Nano Today 37 (2021) 101063

as environmental monitoring, food safety, and diagnostics where 2) Stability of the nanoarchitectures. For reliable use in some
trace-level detection is required. fields, the nanostructured SERS substrates should not be too
Applications of vertically aligned nanostructures for SERS de­ fragile. Stability regarding multiple factors such as oxidation,
tection of diverse hazardous or toxic chemicals have been reported. heating, light exposure, pH, and ionic strength should be con­
For instance, He et al. analyzed explosive compounds such as piciric sidered.
acid (PA) and 3-nitro-1,2,4-triazol-5-one (NTO) on superhydrophobic 3) Analyte diffusion and concentration. Along with the develop­
Ag pillar arrays [39] while Li et al. detected trinitrotoluene (TNT) on ment of novel, unique nanostructures, the diffusion and con­
Ag-nanoparticle decorated polyacrylonitrile nanohump arrays [52]. centration behavior of analytes should be thoroughly
The latter work also reported the detection of an environmental investigated. It is highly desirable to develop new methods to
pollutant called polychlorinated biphyenyls (PCBs) that was also control the position of analytes and enrich a locally concentrated
demonstrated by Huang et al. using Ag-capped Au nanpillar arrays area with analytes in sophisticated nanoarchitectures.
[65] and by Tang et al. with cone-shaped ZnO nanorod arrays de­ Furthermore, it remains challenging to create a platform to detect
corated with Ag nanoparticles [69]. Similarly, Kandjani et al. de­ a wide variety of analytes at different material phases with high
tected the Hg ions as water pollutants using ZnO/Ag nanoarrays sensitivity such as liquid, solid, or even gas phase.
[129]. Food contaminants were also examined by Wang et al. who 4) Selective and specific detection. The “fingerprint” recognition
detected common pesticide residues of thiram (TMTD), methyl capability of SERS may be challenging in a complex matrix due to
parathion (MPT), and malachite green (MG) on a 3D PDMS nano­ signal interference and capturing specific molecules onto the
tentacle array covered with Ag nanoparticles [54]. The detection of substrate is required. Therefore, plasmonic nanostructures are
melamine, often found in milk, was demonstrated by Zhang et al. expected to achieve molecular selectivity, which can be obtained
using 3D “sunflower-like” nanoarrays decorated with Ag nano­ by functionalization of antibodies, enzymes, aptamers, molecu­
particles [181]. larly imprinted polymers, and chemical ligands. Such functiona­
Trace-level detection of biomolecules ranging from hormones, lization strategies can promote nanostructures towards rapid and
proteins, or cells are essential for diagnosis of diseases at an early reliable SERS detection with molecular selectivity and specificity.
stage with high accuracy. Detection of such biomolecules using 5) Extension of applications. With improved understanding of
SERS-based techniques is a promising method to benefit the field of vertically structured SERS substrates and their applications, new
diagnostics. For example, nM level detection of DNA and RNA base innovations can be achieved in other research fields as well. For
molecules has been reported using highly uniform nanoparticle ar­ example, multimodal sensing, 3D photonic crystals, antireflective
rays [35], nanopillar arrays [123], and 3D nanostar dimers [190,191]. structures, optical resonators, and hyperspectral and high-speed
Several different neurotransmitter molecules have been detected Raman imaging can be further developed with the assistance of
such as methylparathion [128], dopamine, serotonin [155], and va­ high-performance SERS.
sopressin [201]. Research shows that the detection of biomarkers
has been reported at concentrations critical for diagnosis; glucose CRediT authorship contribution statement
for diabetes [103], amyloid beta for Alzheimer’s disease [27,135], and
calcium dipicolinate for anthrax [122]. Other than small molecules, Yang Liu: Design, Conceptualization, Writing - original draft.
Zhao et al. [29,30] and Huang et al. [31] successfully demonstrated Minjoon Kim: Writing - review & editing. Seunghee H. Cho:
the detection of long DNA strands, which are difficult to detect using Writing - review & editing. Yeon Sik Jung: Writing - review &
conventional planar SERS substrates, using vertically aligned na­ editing, Supervision, Funding acquisition.
nostructures. Further application to larger biomolecules has been
demonstrated using nanopillar arrays for the detection of bacterial Declaration of Competing Interest
pathogens [133] and 3D nanooctahedra for cancer cell analysis [88].
The authors declare that they have no known competing fi­
Conclusion and future perspective nancial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Surface-enhanced Raman spectroscopy has been extensively
studied because of its ultra-high sensitivity and wide range of ap­ Acknowledgements
plications in qualitative and quantitative analysis. As a consequence,
structurally uniform substrates with high sensitivity, stability, and This work was supported by the National Research Foundation of
signal reproducibility are highly desired. Recently, vertically aligned Korea (NRF) grant funded by the Ministry of Science and ICT (MSICT)
nanoarchitectures have drawn considerable attention thanks to the (No. 2019R1A2C2086240).
development of nanofabrication techniques and improved under­
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platform consisting of 3D Sub-10 nm annular hot spots for ultrasensitive SERS Group at Korea Advanced Institute of Science and
detection, Adv. Opt. Mater. 6 (2018) 1800056. Technology (KAIST) as a Postdoctoral Researcher. He is
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SERS performance in 3D “sunflower-like” nanoarrays decorated with Ag na­ Science from 2020. His research focuses on ultrasensitive
noparticles, Nanoscale 9 (2017) 3114–3120. detection and water purification with 3D nanostructured
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[184] M. Chirumamilla, A. Chirumamilla, A.S. Roberts, R.P. Zaccaria, F. De Angelis,
P.K. Kristensen, R. Krahne, S.I. Bozhevolnyi, K. Pedersen, A. Toma, Hot-spot
engineering in 3D multi-branched nanostructures: ultrasensitive substrates for Minjoon Kim received his B.S. in Materials Science and
surface-enhanced Raman spectroscopy, Adv. Opt. Mater. 5 (2017) 1600836. Engineering at Korea Advanced Institute of Science and
[185] Y. Fang, N.-H. Seong, D.D. Dlott, Measurement of the distribution of site en­ Technology (KAIST) in 2019. He is a master student in
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[186] E.C.L. Ru, P.G. Etchegoin, M. Meyer, Enhancement factor distribution around a focuses on the development and application of plas­
single surface-enhanced Raman scattering hot spot and its relation to single monic nanostructures for SERS.
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[187] N.A. Hatab, C.M. Rouleau, S.T. Retterer, G. Eres, P.B. Hatzinger, B. Gu, An in­
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strates for energetics detection, Analyst 136 (2011) 1697–1702.
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B.H. Gu, Free-standing optical gold bowtie nanoantenna with variable gap size
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Seunghee H. Cho received her B.S. degree in Materials
[190] M. Chirumamilla, A. Toma, A. Gopalakrishnan, G. Das, R.P. Zaccaria, R. Krahne,
Science and Engineering at Hanyang University in 2016
E. Rondanina, M. Leoncini, C. Liberale, F. De Angelis, E. Di Fabrizio, 3D nanostar
and her M.S. degree in Materials Science and Engineering
dimers with a sub-10 nm gap for single-/few-molecule surface-enhanced
at Korea Advanced Institute of Science and Technology
Raman scattering, Adv. Mater. 26 (2014) 2353–2358.
(KAIST) in 2018. She is currently a graduate student re­
[191] A. Gopalakrishnan, M. Chirumamilla, F. De Angelis, A. Toma, R.P. Zaccaria,
searcher in Prof. Yeon Sik Jung's group at KAIST, focusing
R. Krahne, Bimetallic 3D nanostar dimers in ring cavities: recyclable and robust
on the application of surface-enhanced Raman spectro­
surface-enhanced Raman scattering substrates for signal detection from few
scopy to trace-level detection.
molecules, ACS Nano 8 (2014) 7986–7994.
[192] M. Chirumamilla, A. Gopalakrishnan, A. Toma, R. Proietti Zaccaria, R. Krahne,
Plasmon resonance tuning in metal nanostars for surface enhanced Raman
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[193] D. Wang, W. Zhu, M.D. Best, J.P. Camden, K.B. Crozier, Directional Raman
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13 (2013) 2194–2198.
[194] A. Ahmed, R. Gordon, Directivity enhanced Raman spectroscopy using na­
noantennas, Nano Lett. 11 (2011) 1800–1803. Prof. Yeon Sik Jung is a full professor at the Dept. of
[195] H.Y. Zhao, J. Jin, W.J. Tian, R. Li, Z. Yu, W. Song, Q. Cong, B. Zhao, Y. Ozaki, Three- Materials Science and Engineering of Korea Advanced
dimensional superhydrophobic surface-enhanced Raman spectroscopy sub­ Institute of Science and Technology (KAIST). His research
strate for sensitive detection of pollutants in real environments, J. Mater. Chem. area includes sub-10 nm nanofabrication based on directed
A 3 (2015) 4330–4337. self-assembly of block copolymers and nanotransfer-
[196] X. Li, H.K. Lee, I.Y. Phang, C.K. Lee, X.Y. Ling, Superhydrophobic-oleophobic Ag printing, printable sensor devices, nanopatterned 3D cata­
nanowire platform: an analyte-concentrating and quantitative aqueous and lysts, 2-dimensional nanostructures, and quantum-dot
organic toxin surface-enhanced Raman scattering sensor, Anal. Chem. 86 optoelectronic devices. He has published more than 130
(2014) 10437–10444. journal papers and earned more than 45 patents including
[197] F. Xu, Y. Zhang, Y. Sun, Y. Shi, Z. Wen, Z. Li, Silver nanoparticles coated zinc oxide 7 US patents mostly in the field of nanofabrication and
nanorods array as superhydrophobic substrate for the amplified SERS effect, devices. He received his Ph.D. degree (2009) in materials
J. Phys. Chem. C. 115 (2011) 9977–9983. science and engineering from MIT (Massachusetts Institute
[198] C.H. Zhu, G.W. Meng, P. Zheng, Q. Huang, Z.B. Li, X.Y. Hu, X.J. Wang, Z.L. Huang, of Technology).
F.D. Li, N.Q. Wu, A hierarchically ordered array of silver-nanorod bundles for

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