Bala Krishna Juluri

A Mechanical Actuator Driven Electrochemically by Artificial Molecular Muscles

A microcantilever, coated with a monolayer of redox-controllable, bistable [3]rotaxane molecules (artificial molecular muscles), undergoes reversible deflections when subjected to alternating oxidizing and reducing electrochemical potentials. The microcantilever devices were prepared by precoating one surface with a gold film and allowing the palindromic [3]rotaxane molecules to adsorb selectively onto one side of the microcantilevers, utilizing thiol-gold chemistry. An electrochemical cell was employed in the experiments, and deflections were monitored both as a function of (i) the scan rate (< or =20 mV s(-1)) and (ii) the time for potential step experiments at oxidizing (>+0.4 V) and reducing (<+0.2 V) potentials. The different directions and magnitudes of the deflections for the microcantilevers, which were coated with artificial molecular muscles, were compared with (i) data from nominally bare microcantilevers precoated with gold and (ii) those coated with two types of control compounds, namely, dumbbell molecules to simulate the redox activity of the palindromic bistable [3]rotaxane molecules and inactive 1-dodecanethiol molecules. The comparisons demonstrate that the artificial molecular muscles are responsible for the deflections, which can be repeated over many cycles. The microcantilevers deflect in one direction following oxidation and in the opposite direction upon reduction. The approximately 550 nm deflections were calculated to be commensurate with forces per molecule of approximately 650 pN. The thermal relaxation that characterizes the devices deflection is consistent with the double bistability associated with the palindromic [3]rotaxane and reflects a metastable contracted state. The use of the cooperative forces generated by these self-assembled, nanometer-scale artificial molecular muscles that are electrically wired to an external power supply constitutes a seminal step toward molecular-machine-based nanoelectromechanical systems (NEMS).

Systematic investigation of localized surface plasmon resonance of long-range ordered Au nanodisk arrays

Ordered Au nanodisk arrays were fabricated on glass substrates using nanosphere lithography combined with a two-step reactive ion etching technique. The optical properties of these arrays were investigated both experimentally and theoretically. Specifically, the effects of disk diameter on localized surface plasmon resonance (LSPR) were characterized and compared with results from discrete dipole approximation (DDA) calculations. The effects of glass substrate, Cr interfacial layer, and Au thickness on LSPR were investigated computationally. Furthermore, thermal treatment was found to be essential in improving the nanodisk arrays’ LSPR properties. Using atomic force microscopy and DDA calculations, it was established that the improvements in LSPR properties were due to thermally induced morphologic changes. Finally, microfluidic channels were integrated with the annealed disk arrays to study the sensitivity of LSPR to the change in surroundings’ refractive index. The dependence of LSPR on surroundings’ refractive index was measured and compared with calculated results.

Dynamic Tuning of Plasmon–Exciton Coupling in Arrays of Nanodisk–J‐aggregate Complexes

Y.B.Z and B.K.J contributed equally to this work. This research was supported by the Air Force Office of Scientific Research (FA9550-08-1-0349), the National Science Foundation (ECCS-0801922, ECCS-0609128, and ECCS-0609128), and the Penn State Center for Nanoscale Science (MRSEC). Components of this work were conducted at the Pennsylvania State University node of the NSF-funded National Nanotechnology Infrastructure Network. Y.B.Z. recognizes the support from KAUST Scholar Award and the Founders Prize and Grant of the American Academy of Mechanics. The authors thank I-Kao Chiang, Aitan Lawit and Thomas R. Walker for helpful discussions.

Frequency-addressed tunable transmission in optically thin metallic nanohole arrays with dual-frequency liquid crystals

Frequency-addressed tunable transmission is demonstrated in optically thin metallic nanohole arrays embedded in dual-frequency liquid crystals (DFLCs). The optical properties of the composite system are characterized by the transmission spectra of the nanoholes, and a prominent transmission peak is shown to originate from the resonance of localized surface plasmons at the edges of the nanoholes. An ∼17 nm shift in the transmission peak is observed between the two alignment configurations of the liquid crystals. This DFLC-based active plasmonic system demonstrates excellent frequency-dependent switching behavior and could be useful in future nanophotonic applications.

Propagation of designer surface plasmons in structured conductor surfaces with parabolic gradient index

In this work, we investigate the propagation of designer surface plasmons in planar perfect electric conductor structures that are subject to a parabolic graded-index distribution. A three-dimensional, fully vectorial finite-difference time-domain method was used to engineer a structure with a parabolic effective group index by modulating the dielectric constant of the structures square holes. Using this structure in our simulations, the lateral confinement of propagating designer surface plasmons is demonstrated. Focusing, collimation and waveguiding of designer plasmons in the lateral direction is realized by changing the width of the source beam. Our findings contribute to applications of designer surface plasmons that require energy concentration, diffusion, guiding, and beam aperture modification within planar perfect electric conductors. .

Scalable Manufacturing of Plasmonic Nanodisk Dimers and Cusp Nanostructures using Salting-out Quenching Method and Colloidal Lithography

Localization of large electric fields in plasmonic nanostructures enables various processes such as single-molecule detection, higher harmonic light generation, and control of molecular fluorescence and absorption. High-throughput, simple nanofabrication techniques are essential for implementing plasmonic nanostructures with large electric fields for practical applications. In this article we demonstrate a scalable, rapid, and inexpensive fabrication method based on the salting-out quenching technique and colloidal lithography for the fabrication of two types of nanostructures with large electric field: nanodisk dimers and cusp nanostructures. Our technique relies on fabricating polystyrene doublets from single beads by controlled aggregation and later using them as soft masks to fabricate metal nanodisk dimers and nanocusp structures. Both of these structures have a well-defined geometry for the localization of large electric fields comparable to structures fabricated by conventional nanofabrication techniques. We also show that various parameters in the fabrication process can be adjusted to tune the geometry of the final structures and control their plasmonic properties. With advantages in throughput, cost, and geometric tunability, our fabrication method can be valuable in many applications that require plasmonic nanostructures with large electric fields.

Metallic Membranes with Subwavelength Complementary Patterns: Distinct Substrates for Surface-Enhanced Raman Scattering

We present a detailed comparison of surface-enhanced Raman spectroscopy (SERS) signals from metallic nanoparticle arrays and their complementary hole arrays. Using an analytical model for local field enhancement, we show that the SERS enhancements of the hole arrays are closely related to their transmission spectra. This trend is experimentally confirmed and characterized by a cos(4 )θ dependence of the SERS signal on the excitation polarization angle θ. The particle arrays, on the other hand, exhibit quite different behavior because of the existence of considerable evanescent modes in the near field. Their maximal local field gains appear at wavelengths generally much larger than their localized surface plasmonic resonant wavelengths.

Beam aperture modifier and beam deflector using gradient-index photonic crystals

We designed and simulated a beam aperture modifier and a beam deflector using two-dimensional parabolic gradient-index (GRIN) photonic crystals (PCs). The GRIN PCs are composed of dielectric columns with graded radii along the direction transverse to propagation. Both finite-difference time-domain methods and gradient optics analytical solutions were used to characterize the change in beam width and propagation direction. Multifunctional GRIN PCs combining both beam aperture modification and beam deflection were also designed and simulated. These GRIN PC based designs can be used as optical connectors and bidirectional waveguide couplers in applications such as miniaturized photonic integrated circuits.

Shifts in plasmon resonance due to charging of a nanodisk array in argon plasma

A method for generating charge-induced plasmonic shifts, using argon plasma to charge nanoparticle arrays, is presented. Particles develop a negative charge, due to enhanced collisions with high-temperature electrons, in low-temperature plasmas. The negative charge generated causes a blue shift in the localized surface plasmon resonance. The dynamics of the shift were recorded and discussed. This effect could be used as a real-time method for studying the dynamics for charging in plasma.

Simple fabrication of snowman-like colloids

Anisotropic colloidal particles consisting of different compositions and geometry are useful for various applications. These include optical biosensing, antireflective coatings and electronic displays. In this work we demonstrate a simple and cost-effective method for fabricating anisotropic colloidal particles bearing a snowman-like shape. This is achieved by first settling the positively-charged polystyrene latex (PSL) colloids and negatively-charged silica colloids in deionized water onto a glass substrate, forming heterodoublets. The temperature is then raised above the glass transition temperature of the polymer. As a result, the silica particle spontaneously rises to the top of the PSL particle forming a snowman like structure. We have extended this method to different sizes and shown that the structure of the hybrid particles can be tuned by adjusting the size ratio between the silica and the PSL colloids. The surface coverage of the PSL, and hence of the snowman particles, on the glass substrate can also be varied by changing the ionic strength of the solution during the adhesion of PSL to the glass.