LETTER

pubs.acs.org/NanoLett

Omnidirectional 3D Nanoplasmonic Optical Antenna Array

via Soft-Matter Transformation
Benjamin M. Ross,† Liz Y. Wu,† and Luke P. Lee*
Applied Science and Technology Graduate Group, Biomolecular Nanotechnology Center, and Berkeley Sensor and Actuator Center,
and Department of Bioengineering, University of California-Berkeley, Berkeley, California 94720, United States
bS Supporting Information
ABSTRACT: Inspired by the natural processes during mor-
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phogenesis, we demonstrate the transformation capability of

active soft-matter to define nanoscale metal-on-polymer archi-
tectures below the resolution limit of conventional lithography.
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Specifically, using active polymers, we fabricate and characterize

ultradense nanoplasmonic antenna arrays with sub-10 nm tip-
to-tip nanogaps. In addition, the macroscale morphology can be
independently manipulated into arbitrary three-dimensional geometries, demonstrated with the fabrication of an omnidirectional
nanoplasmonic optical antenna array.
KEYWORDS: Nanoplasmonics, soft-matter, active polymers, nanosphere lithography, nanogap, omnidirectional antenna

S hape-changing polymers, also called active or smart polymers,

have been studied in recent years for their ability to deform
significantly on the macro-scale when a stimulus is applied. Such
Active polymers can be readily deformed into complex 3D
geometries at the macroscale, while the nanoscale morphology is
retained on the polymer surface. This provides a platform for
stimulus may come in the form of thermal, electric, magnetic, or integrating nanoarchitectures into stretchable devices ranging
optical excitation.1
3 Several research groups have demonstrated from flexible displays, to bioinspired lenses, and to biomedical
microfabrication techniques taking advantage of active poly- systems.12 We demonstrate an omnidirectional nanoplasmonic
mers.4
6 However, most work has focused on microscale fea- antenna array in Figure 1e. The 3D structure is achieved by heating
tures, and nanofabrication via active polymers has primarily the contracted polymer until it is moldable (process shown in
focused on generation of random structures such as wrinkles7 Supporting Information Figure 2), and its optical properties are
with the exception of recent work by Odom’s group.8 The discussed below.
control of arbitrarily defined nanoscale structures via active Both the nano- and macroscale deformations of active polymers
polymers has remained a challenge, and many important ques- are well-suited to the needs of nanoplasmonic molecular sensors. In
tions remain regarding both the limits of this technique and this application, collective electron oscillations of metallic nanos-
properties of the resulting nanostructures. Here, we extend our tructures cause extremely high local electric fields, which can then
earlier work9 and demonstrate that uniform polymer deforma- be used to provide a spectroscopic signal in the form of localized
tions can be engineered to create high-density nanogap structures surface plasmon resonance (LSPR) shift,13 surface-enhanced Ra-
comparable to the resolution limit of high-resolution lithographic man scattering (SERS),14 surface-enhanced fluorescence (SEF),15
methods. Control of deformation at the nanoscale allows the or plasmon resonance energy transfer (PRET).16 Because the
possibility of fabricating complex nanostructures in a way com- sensitivity of such structures is closely related to the nanostruc-
parable to that achieved naturally during morphogenesis, as illu- ture geometry, the nanogap distance between structures, and the
strated in Figure 1a
d. Specifically, the contraction of an active density of such structures,17,18 active substrates offer the possi-
polymer substrate allows nanostructure repositioning in a way bility of creating a new class of highly sensitive nanoplasmonic
analogous to apical constriction during morphogenesis (process sensors. In addition, the local electromagnetic field controlled by
shown in Supporting Information Figure 1). The ability to nanoplasmonic antennas can be used to create new light sources,
control substrate dimensions after deposition of structures can for example, through second harmonic generation effects.19
confer the significant advantages over standard rigid substrates Because the needs of nanoplasmonics are well-suited to the
that biology has achieved,10,11 such as (i) the potential to alter advantages of active polymer nanofabrication, we use nanoplas-
structure-to-structure distance, surpassing both resolution and monics as a proof-of-concept and demonstrate active polymer
structural density of the initial placement, and (ii) the potential to nanofabrication for creating ultradense nanoplasmonic antenna arrays
deform nanostructures into complex three-dimensional (3D) with sub -10 nm tip-to-tip distances. The nanoprisms are defined with
geometries. The former benefit is of wide interest in reducing nanosphere lithography, which has been demonstrated to be a
feature size of devices, while the latter is of particular interest in
microelectromechanical and nanoelectromechanical systems Received: December 27, 2010
fabrication. Published: June 10, 2011

r 2011 American Chemical Society 2590 dx.doi.org/10.1021/nl201516g | Nano Lett. 2011, 11, 2590–2595
Nano Letters LETTER

Figure 1. (a,b) Schematic of natural structure definition due to apical constriction; (c,d) biologically inspired transformation of metal-on-polymer
structures for defining nanostructure morphology; (e) omnidirectional nanoplasmonic antenna arrays; inset shows the nanoprism arrays, which are
present at each “pixel” of the lens. Panels a,b reprinted by permission from Macmillan Publishers Ltd.: Nature Reviews Molecular Cell Biology 8,
633, Copyright 2007.

well-characterized and cost-effective method for patterning na- potentially reduce the polymer area to 4% and is a clear area of
noplasmonic materials over large areas.20 The size and periodi- future focus to improve the technique presented here. The
city of the nanoprisms can be tuned by choice of the nanosphere reduction in area from the active polymer contraction allows
size. In addition, no high temperatures or corrosive chemicals are the formation of nanostructures in densities above that which are
required, which makes processing fully compatible with the initially defined, regardless of the initial fabrication technique.
active polymer substrate used. After the nanoprisms are defined, Concomitant with the increase in density is the potential to
the polymer is contracted via thermal activation (process shown create nanogaps between lithographically defined structures. In
in Supporting Information Figure 1). In this work, the nano- Figure 2d
f, we illustrate the nanogap formation in more detail
spheres are drop-cast, which provides defect-free regions on the for nanoprisms lengths of 120 nm to 1.6 μm. The nanogaps in
order of 100 μm2. While regions of this size are sufficient for the Figure 2f are clearly sub-10 nm, comparable to the limit of high-
characterization in this study, much larger areas of nanosphere resolution techniques such as electron beam lithography and
arrays are achievable, using spin coating, liquid surface self- focused ion beam (FIB) techniques. While the precision is likely
assembly, dip drying, and colloid confinement methods.21,22 to be higher for these conventional techniques, the low-cost and
The increase in density of the nanoprisms is defined by the highly multiplexed capability of active polymer nanofabrication
contraction the active polymer, which for the polystyrene poly- give this technique an advantage for many practical applications.
mer substrate studied is approximately 14% of its original area. Nanogap formation allows the creation of tip-to-tip nanopr-
For the nanoprism arrays studied here, this strain is sufficient to ism structures (also called bow-ties), which have shown to be
create nanogaps and significant change in optical properties, but excellent substrates for localizing electromagnetic fields.24 Since
we note that larger strains (and hence increase in nanostructure the local electromagnetic field increases with decreasing nanogap
density) are achievable; for example, a 500% strain has been distance between the nanoprisms, contracting the substrates should
demonstrated using triblock liquid crystal polymers,23 which would allow for significantly increased molecular sensitivity, as well as
2591 dx.doi.org/10.1021/nl201516g |Nano Lett. 2011, 11, 2590–2595
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Figure 2. Active polymer fabrication of nanoprism arrays: (a
c) finite element simulation of electric field amplitude surrounding initial and contracted
nanoprism arrays; (d
f) SEM images of nanogaps between gold nanoprisms of different sizes. Nanoprism lengths are approximately (d) 1.6 μm,
(e) 540 nm, and (f) 120 nm.

enhancing nonlinear effects such as second harmonic generation. another mechanism, such as delamination. The effect of increas-
Using finite element simulation, we show the order-of-magnitude ing the thickness of the gold layer is also predicted by eq 1. Since
improvement in local field enhancement upon contraction in the critical buckling stress is proportional to the second power of
Figure 2a
c. the nanoprism thickness, thicker films result in reduced buckling
We next consider how deformation of the nanoprisms varies at for a given size. These predictions match well with experiment; as
different length scales. As shown in Figure 3, the final substrate shown in Figure 3a, buckling is clearly visible for larger and thinner
morphology is sensitive to the initial nanostructure size and nanoprisms, while smaller and thicker prisms tend to delaminate
thickness, and buckling and delamination regimes can be dis- from the surface and “stand up.”
tinguished. Assuming the mismatch strain between the gold nano- We note that the useful increases in density, nanogap creation,
prisms and the polymer to be the strain induced by the con- and deformation are partially offset by a decrease in the order of
tracting polymer, and the modulus E = 78 GPa and Poisson ratio the system; variations in the contraction behavior of the active
ν = 0.44 for gold, the mismatch stress between the nanostruc- polymer cause some defects to occur in the resulting nanoprism
tures and the polymer is σm =
52 GPa. The thin Ti adhesion array. However, this is not a fundamental limitation, and future
layer, used to improve adhesion between the substrate and the improvements in the uniformity of the polymer substrate may
gold nanoprisms, can be ignored in this approximation, since it is allow a reduction in the defects observed. Future research is needed
much thinner than the gold layer, and because the relevant to clarify the fundamental limits at which active polymers may
mechanical properties cause a very similar buckling response for uniformly contract, and how these limits depend on the form of
Ti and Au in the size regime considered. activation (thermal, electrical, etc.).
The buckling regimes can be understood using a simple intuitive The changes in substrate morphology are correlated with
model. Consider the formula for buckling of a circular patch of a distinct changes in optical properties. Since the size and periodi-
thin film25 city of nanoprisms created by nanosphere lithography are not
Ef h2f traditionally independent, active polymer nanofabrication allows
σ b ¼
1:2235 ð1Þ a separate handle for tuning nanoprism periodicity, and hence
a2 tunability of their spectra. Tunability is an essential characteristic
where σb is the critical stress for the lowest axially symmetric of any plasmonic architecture designed for molecular detection;
buckling mode, Ef is the plane strain modulus, hf is the film first, because tuning resonance to the “biological window” is
thickness, a is the debonded radius, and the negative sign indicates a necessary to prevent cellular damage, and second, because tuning
compressive stress. This formula is a simplification of the experi- to the vicinity of specific molecular resonances can create large
mental case studied: an infinite film is assumed (compared to the increases in both SERS26 and LSPR-shift27 signals. As shown in
experimental condition of finite nanoprisms) and the debonded Figure 4, the extinction peak is blueshifted 200
300 nm upon
region is assumed to be circular. Nonetheless, the theory pro- contraction with thicker nanoprisms exhibiting a greater blueshift
vides a useful intuitive picture of the physical scenario, and the after contraction.
results agree to an order-of-magnitude with experiment. Three effects contribute to the observed blueshift. Radiative
The results of eq 1 are shown in Figure 3b,c. The stress mis- dipole interactions between the nanoprisms cause a blueshift as
match allows for buckling to occur until a critical size is reached. the lattice spacing is decreased.28 In addition, touching nanopr-
Below this critical size, the stress required for buckling is higher isms are no longer electrically isolated, again resulting in a blueshift.
than the stress mismatch, and the stress must be relieved by Finally, the deformation of individual nanoprisms may also con-
2592 dx.doi.org/10.1021/nl201516g |Nano Lett. 2011, 11, 2590–2595
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Figure 3. Matrix of the morphology achieved for varying gold nanoprism size and thickness: (a) representative SEM images; the different regimes of
buckling and delamination can be understood with a basic analytical model shown in (b) and (c), as predicted by eq 1.

tribute to the observed shift. More study is needed to precisely nanoplasmonic antenna lens. SEM images verified the local nano-
determine the relative importance of each of these effects. We scale morphology is not noticeably affected by macroscopic
note that for small and thick nanoprisms (s = 95 nm, h = 45 nm in deformation (Supporting Information Figure 3). By integrating
Figure 4a), the lack of a uniform nanostructure prevents a clear such devices with flexible electronics12 in future device iterations,
extinction peak from emerging for the contracted polymer, con- individual pixels may be addressed simultaneously, thus achiev-
sistent with the lack of buckling deformation in this regime. ing a “plasmonic compound eye.”
As discussed above, the contracted polymer substrates can be To conclude, we have proposed a biologically inspired mor-
readily molded into 3D shapes, such as the lens shown in Figure 1e. phogenetic transformation of hybrid metal and polymer struc-
We show the uniformity of spectra taken from different pixels of tures for defining nanostructure morphology and have demonstrated
this substrate in Figure 4b. The pixel configuration was achieved its utility in creating omnidirectional nanoplasmonic antenna arrays.
using a stainless steel shadow mask (Fotofab), which served as a Active polymer nanofabrication allows the potential to alter
physical barrier during gold deposition, and spectra from in- structure-to-structure distance down to sub-10 nm, surpassing
dividual pixels were achieved using a microscope (Zeiss Axiovert both resolution and structural density of the initial placement. In
200) and spectrophotometer (Princeton Instruments Acton addition, polymer molding offers macroscopic deformation of
SP2300). For each pixel, a spectrum was taken over approxi- plasmonic architectures into arbitrary 3D geometries. We have
mately a 100 μm2 area, and the position of the pixel was recorded. demonstrated the size-dependent mechanical response of nano-
Despite the significant change in structure curvature on the plasmonic prism antenna arrays fabricated with active polymer
macroscale, the spectra obtained from varying positions on the fabrication and have correlated the results with analytic theory.
lens are nearly identical; hence, we have achieved an omnidirectional Finally, we have correlated the changes in morphology with optical
2593 dx.doi.org/10.1021/nl201516g |Nano Lett. 2011, 11, 2590–2595
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Figure 4. Optical changes with substrate contraction: (a) (left) schematic of nanoprism contraction and (right) representative extinction spectra of
nanoprism arrays before (solid line) and after contraction (dashed line) for varying nanoprism size and height; (b) extinction spectra taken with varying
ϕ and θ positions demonstrate the uniformity of pixels in the omnidirectional nanoplasmonic antenna lens shown in inset.

response. We believe active polymer-based nanofabrication will ’ ACKNOWLEDGMENT

have wide utility for developing high-density device architectures This work was funded by The National Institutes of Health
for optical MEMS, NEMS, and nanoplasmonic devices and Nanomedicine Development Center for the Optical Control of
optical systems. Biological Function (PN2 EY018241), and the Center for
Nanostructured Materials Technology under “21st Century
Frontier R&D Programs” of the Ministry of Education, Science,
’ ASSOCIATED CONTENT and Technology, Korea. B.M.R. acknowledges support from The
Berkeley Fellowship. L.Y.W. acknowledges support from a
bS Supporting Information. Description and figures of ex- Taiwan Merit Scholarship.
perimental and numerical methods. This material is available free
of charge via the Internet at http://pubs.acs.org.
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