Plasmonic molecules are building blocks of metallic nanostructures that give rise to intriguing optical phenomena with similarities to those seen in molecular systems. The ability to design plasmonic hybrid structures and molecules with nanometric resolution would enable applications in optical metamaterials and sensing that presently cannot be demonstrated, because of a lack of suitable fabrication methods allowing the structural control of the plasmonic atoms on a large scale. Here we demonstrate a wafer-scale “lithography-free” parallel fabrication scheme to realize nanogap plasmonic meta-molecules with precise control over their size, shape, material, and orientation. We demonstrate how we can tune the corresponding coupled resonances through the entire visible spectrum. Our fabrication method, based on glancing angle physical vapor deposition with gradient shadowing, permits critical parameters to be varied across the wafer and thus is ideally suited to screen potential structures. We obtain billions of aligned dimer structures with controlled variation of the spectral properties across the wafer. We spectroscopically map the plasmonic resonances of gold dimer structures and show that they not only are in good agreement with numerically modeled spectra, but also remain functional, at least for a year, in ambient conditions.
4th IEEE International Conference on Manipulation, Automation and Robotics at Small Scales (MARSS), July 2019 (conference)
Remotely controlled, automated actuation and manipulation at the microscale is essential for a number of micro-manufacturing, biology, and lab-on-a-chip applications. To transport and manipulate micro-objects, arrays of remotely controlled micro-actuators are required, which, in turn, typically require complex and expensive solid-state chips. Here, we show that a continuous surface can function as a highly parallel, many-degree of freedom, wirelessly-controlled microactuator with seamless deformation. The soft continuous surface is based on a hydrogel that undergoes a volume change in response to applied light. The fabrication of the hydrogels and the characterization of their optical and thermomechanical behaviors are reported. The temperature-dependent localized deformation of the hydrogel is also investigated by numerical simulations. Static and dynamic deformations are obtained in the soft material by projecting light fields at high spatial resolution onto the surface. By controlling such deformations in open loop and especially closed loop, automated photoactuation is achieved. The surface deformations are then exploited to examine how inert microbeads can be manipulated autonomously on the surface. We believe that the proposed
approach suggests ways to implement universal 2D micromanipulation schemes that can be useful for automation in microfabrication and lab-on-a-chip applications.
Collins, J., Rusimova, K., Hooper, D., Jeong, H. H., Ohnoutek, L., Pradaux-Caggiano, F., Verbiest, T., Carbery, D., Fischer, P., Valev, V.
Phys. Rev. X, 9(011024), January 2019 (article)
Chiral nano- or metamaterials and surfaces enable striking photonic properties, such as negative refractive index and superchiral light, driving promising applications in novel optical components, nanorobotics, and enhanced chiral molecular interactions with light. In characterizing chirality, although nonlinear chiroptical techniques are typically much more sensitive than their linear optical counterparts, separating true chirality from anisotropy is a major challenge. Here, we report the first observation of optical activity in second-harmonic hyper-Rayleigh scattering (HRS). We demonstrate the effect in a 3D isotropic suspension of Ag nanohelices in water. The effect is 5 orders of magnitude stronger than linear optical activity and is well pronounced above the multiphoton luminescence background. Because of its sensitivity, isotropic environment, and straightforward experimental geometry, HRS optical activity constitutes a fundamental experimental breakthrough in chiral photonics for media including nanomaterials, metamaterials, and chemical molecules.
Wu, Z., Troll, J., Jeong, H. H., Wei, Q., Stang, M., Ziemssen, F., Wang, Z., Dong, M., Schnichels, S., Qiu, T., Fischer, P.
Science Advances, 4(11):eaat4388, November 2018 (article)
The intravitreal delivery of therapeutic agents promises major benefits in the field of ocular medicine. Traditional delivery methods rely on the random, passive diffusion of molecules, which do not allow for the rapid delivery of a concentrated cargo to a defined region at the posterior pole of the eye. The use of particles promises targeted delivery but faces the challenge that most tissues including the vitreous have a tight macromolecular matrix that acts as a barrier and prevents its penetration. Here, we demonstrate novel intravitreal delivery microvehicles slippery micropropellers that can be actively propelled through the vitreous humor to reach the retina. The propulsion is achieved by helical magnetic micropropellers that have a liquid layer coating to minimize adhesion to the surrounding biopolymeric network. The submicrometer diameter of the propellers enables the penetration of the biopolymeric network and the propulsion through the porcine vitreous body of the eye over centimeter distances. Clinical optical coherence tomography is used to monitor the movement of the propellers and confirm their arrival on the retina near the optic disc. Overcoming the adhesion forces and actively navigating a swarm of micropropellers in the dense vitreous humor promise practical applications in ophthalmology.
Paria, D., Jeong, H. H., Vadakkumbatt, V., Deshpande, P., Fischer, P., Ghosh, A., Ghosh, A.
Nanoscale, 10, pages: 7685-7693, April 2018 (article)
The weak light-matter interaction in graphene can be enhanced with a number of strategies, among which sensitization with plasmonic nanostructures is particularly attractive. This has resulted in the development of graphene-plasmonic hybrid systems with strongly enhanced photodetection efficiencies in the visible and the IR, but none in the UV. Here, we describe a silver nanoparticle-graphene stacked optoelectronic device that shows strong enhancement of its photoresponse across the entire UV spectrum. The device fabrication strategy is scalable and modular. Self-assembly techniques are combined with physical shadow growth techniques to fabricate a regular large-area array of 50 nm silver nanoparticles onto which CVD graphene is transferred. The presence of the silver nanoparticles resulted in a plasmonically enhanced photoresponse as high as 3.2 A W-1 in the wavelength range from 330 nm to 450 nm. At lower wavelengths, close to the Van Hove singularity of the density of states in graphene, we measured an even higher responsivity of 14.5 A W-1 at 280 nm, which corresponds to a more than 10 000-fold enhancement over the photoresponse of native graphene.
In this article, a chiral plasmonic hydrogen‐sensing platform using palladium‐based nanohelices is demonstrated. Such 3D chiral nanostructures fabricated by nanoglancing angle deposition exhibit strong circular dichroism both experimentally and theoretically. The chiroptical properties of the palladium nanohelices are altered upon hydrogen uptake and sensitively depend on the hydrogen concentration. Such properties are well suited for remote and spark‐free hydrogen sensing in the flammable range. Hysteresis is reduced, when an increasing amount of gold is utilized in the palladium‐gold hybrid helices. As a result, the linearity of the circular dichroism in response to hydrogen is significantly improved. The chiral plasmonic sensor scheme is of potential interest for hydrogen‐sensing applications, where good linearity and high sensitivity are required.
Advanced Science, 4(12):1700234, September 2017 (article)
Nanoparticles composed of functional materials hold great promise for applications due to their unique electronic, optical, magnetic, and catalytic properties. However, a number of functional materials are not only difficult to fabricate at the nanoscale, but are also chemically unstable in solution. Hence, protecting nanoparticles from corrosion is a major challenge for those applications that require stability in aqueous solutions and biological fluids. Here, this study presents a generic scheme to grow hybrid 3D nanoparticles that are completely encapsulated by a nm thick protective shell. The method consists of vacuum-based growth and protection, and combines oblique physical vapor deposition with atomic layer deposition. It provides wide flexibility in the shape and composition of the nanoparticles, and the environments against which particles are protected. The work demonstrates the approach with multifunctional nanoparticles possessing ferromagnetic, plasmonic, and chiral properties. The present scheme allows nanocolloids, which immediately corrode without protection, to remain functional, at least for a week, in acidic solutions.
Advanced Materials, 29(30):1701024, June 2017, Back Cover (article)
Nanodiamonds are emerging as nanoscale quantum probes for bio-sensing and imaging. This necessitates the development of new methods to accurately manipulate their position and orientation in aqueous solutions. The realization of an “active” nanodiamond (ND) swimmer in fluids, composed of a ND crystal containing nitrogen vacancy centers and a light-driven self-thermophoretic micromotor, is reported. The swimmer is propelled by a local temperature gradient created by laser illumination on its metal-coated side. Its locomotion—from translational to rotational motion—is successfully controlled by shape-dependent hydrodynamic interactions. The precise engineering of the swimmer's geometry is achieved by self-assembly combined with physical vapor shadow growth. The optical addressability of the suspended ND swimmers is demonstrated by observing the electron spin resonance in the presence of magnetic fields. Active motion at the nanoscale enables new sensing capabilities combined with active transport including, potentially, in living organisms.
Chem. Comm., 52(82):12179-12182, September 2016 (article)
We demonstrate that chiral magnesium nanoparticles show remarkable plasmonic extinction- and chiroptical-effects in the ultraviolet region. The Mg nanohelices possess an enhanced local surface plasmon resonance (LSPR) sensitivity due to the strong dispersion of most substances in the UV region.
Nano Letters, 16(8):4887-4894, July 2016 (article)
Nanoplasmonic systems are valued for their strong optical response and their small size. Most plasmonic sensors and systems to date have been rigid and passive. However, rendering these structures dynamic opens new possibilities for applications. Here we demonstrate that dynamic plasmonic nanoparticles can be used as mechanical sensors to selectively probe the rheological properties of a fluid in situ at the nanoscale and in microscopic volumes. We fabricate chiral magneto-plasmonic nanocolloids that can be actuated by an external magnetic field, which in turn allows for the direct and fast modulation of their distinct optical response. The method is robust and allows nanorheological measurements with a mechanical sensitivity of similar to 0.1 cP, even in strongly absorbing fluids with an optical density of up to OD similar to 3 (similar to 0.1% light transmittance) and in the presence of scatterers (e.g., 50% v/v red blood cells).
Nature Communications, 7, pages: 11331, March 2016 (article)
Biosensors based on the localized surface plasmon resonance (LSPR) of individual metallic nanoparticles promise to deliver modular, low-cost sensing with high-detection thresholds. However, they continue to suffer from relatively low sensitivity and figures of merit (FOMs). Herein we introduce the idea of sensitivity enhancement of LSPR sensors through engineering of the material dispersion function. Employing dispersion and shape engineering of chiral nanoparticles leads to remarkable refractive index sensitivities (1,091 nmRIU(-1) at lambda = 921 nm) and FOMs (>2,800 RIU-1). A key feature is that the polarization-dependent extinction of the nanoparticles is now characterized by rich spectral features, including bipolar peaks and nulls, suitable for tracking refractive index changes. This sensing modality offers strong optical contrast even in the presence of highly absorbing media, an important consideration for use in complex biological media with limited transmission. The technique is sensitive to surface-specific binding events which we demonstrate through biotin-avidin surface coupling.
Google Patents, 2016, WO Patent App. PCT/EP2016/056,377 (patent)
The present invention relates to a method for encapsulating a nanostructure, the method comprising the steps of: -providing a substrate; -forming a plug composed of plug material at said substrate; -forming a nanostructure (on or) at said plug; -forming a shell composed of at least one shell material on external surfaces of the nanostructure, with the at least one shell material covering said nanostructure and at least some of the plug material,whereby the shell and the plug encapsulate the nanostructure. The invention further relates to a coated nanostructure and to the use of a coated nanostructure.
Science Advances, 1(11):e1500501, December 2015 (article)
In the body, mucus provides an important defense mechanism by limiting the penetration of pathogens. It is therefore also a major obstacle for the efficient delivery of particle-based drug carriers. The acidic stomach lining in particular is difficult to overcome because mucin glycoproteins form viscoelastic gels under acidic conditions. The bacterium Helicobacter pylori has developed a strategy to overcome the mucus barrier by producing the enzyme urease, which locally raises the pH and consequently liquefies the mucus. This allows the bacteria to swim through mucus and to reach the epithelial surface. We present an artificial system of reactive magnetic micropropellers that mimic this strategy to move through gastric mucin gels by making use of surface-immobilized urease. The results demonstrate the validity of this biomimetic approach to penetrate biological gels, and show that externally propelled microstructures can actively and reversibly manipulate the physical state of their surroundings, suggesting that such particles could potentially penetrate native mucus.
Adv. Science, 2(7):1500016, 2015, Featured cover article. (article)
A parallel nanolithographic patterning method is presented that can be used to obtain arrays of multifunctional nanoparticles. These patterns can simply be converted into a variety of secondary nanopatterns that are useful for nanolithographic imprint, plasmonic, and etch-mask applications.
In 2014 IEEE 27th International Conference on Micro Electro Mechanical Systems (MEMS), pages: 437-440, January 2014 (inproceedings)
Three-dimensional (3D) fabrication techniques promise new device architectures and enable the integration of more components, but fabricating 3D nanostructures for device applications remains challenging. Recently, we have performed glancing angle deposition (GLAD) upon a nanoscale hexagonal seed array to create a variety of 3D nanoscale objects including multicomponent rods, helices, and zigzags . Here, in an effort to generalize our technique, we present a step-by-step approach to grow 3D nanostructures on more complex nanoseed shapes and configurations than before. This approach allows us to create 3D nanostructures on nanoseeds regardless of seed sizes and shapes.
Controlled local fabrication of three-dimensional (3D) nanostructures is important to explore and enhance the function of single nanodevices, but is experimentally challenging. We present a scheme based on e-beam lithography (EBL) written seeds, and glancing angle deposition (GLAD) grown structures to create nanoscale objects with defined shapes but in aperiodic arrangements. By using a continuous sacrificial corral surrounding the features of interest we grow isolated 3D nanostructures that have complex cross-sections and sidewall morphology that are surrounded by zones of clean substrate.
Our goal is to understand the principles of Perception, Action and Learning in autonomous systems that successfully interact with complex environments and to use this understanding to design future systems