Stephan J. P. Kress

Plasmonic Films Can Easily Be Better: Rules and Recipes

High-quality materials are critical for advances in plasmonics, especially as researchers now investigate quantum effects at the limit of single surface plasmons or exploit ultraviolet- or CMOS-compatible metals such as aluminum or copper. Unfortunately, due to inexperience with deposition methods, many plasmonics researchers deposit metals under the wrong conditions, severely limiting performance unnecessarily. This is then compounded as others follow their published procedures. In this perspective, we describe simple rules collected from the surface-science literature that allow high-quality plasmonic films of aluminum, copper, gold, and silver to be easily deposited with commonly available equipment (a thermal evaporator). Recipes are also provided so that films with optimal optical properties can be routinely obtained.

Direct printing of nanostructures by electrostatic autofocussing of ink nanodroplets

Nanotechnology, with its broad impact on societally relevant applications, relies heavily on the availability of accessible nanofabrication methods. Even though a host of such techniques exists, the flexible, inexpensive, on-demand and scalable fabrication of functional nanostructures remains largely elusive. Here we present a method involving nanoscale electrohydrodynamic ink-jet printing that may significantly contribute in this direction. A combination of nanoscopic placement precision, soft-landing fluid dynamics, rapid solvent vapourization, and subsequent self-assembly of the ink colloidal content leads to the formation of scaffolds with base diameters equal to that of a single ejected nanodroplet. The virtually material-independent growth of nanostructures into the third dimension is then governed by an autofocussing phenomenon caused by local electrostatic field enhancement, resulting in large aspect ratio. We demonstrate the capabilities of our electrohydrodynamic printing technique with several examples, including the fabrication of plasmonic nanoantennas with features sizes down to 50 nm.

Wedge Waveguides and Resonators for Quantum Plasmonics

Plasmonic structures can provide deep-subwavelength electromagnetic fields that are useful for enhancing light–matter interactions. However, because these localized modes are also dissipative, structures that offer the best compromise between field confinement and loss have been sought. Metallic wedge waveguides were initially identified as an ideal candidate but have been largely abandoned because to date their experimental performance has been limited. We combine state-of-the-art metallic wedges with integrated reflectors and precisely placed colloidal quantum dots (down to the single-emitter level) and demonstrate quantum-plasmonic waveguides and resonators with performance approaching theoretical limits. By exploiting a nearly 10-fold improvement in wedge-plasmon propagation (19 μm at a vacuum wavelength, λvac, of 630 nm), efficient reflectors (93%), and effective coupling (estimated to be >70%) to highly emissive (∼90%) quantum dots, we obtain Ag plasmonic resonators at visible wavelengths with quality factors approaching 200 (3.3 nm line widths). As our structures offer modal volumes down to ∼0.004λvac3 in an exposed single-mode waveguide–resonator geometry, they provide advantages over both traditional photonic microcavities and localized-plasmonic resonators for enhancing light–matter interactions. Our results confirm the promise of wedges for creating plasmonic devices and for studying coherent quantum-plasmonic effects such as long-distance plasmon-mediated entanglement and strong plasmon–matter coupling.

Near-Field Light Design with Colloidal Quantum Dots for Photonics and Plasmonics

Colloidal quantum-dots are bright, tunable emitters that are ideal for studying near-field quantum-optical interactions. However, their colloidal nature has hindered their facile and precise placement at desired near-field positions, particularly on the structured substrates prevalent in plasmonics. Here, we use high-resolution electro-hydrodynamic printing (<100 nm feature size) to deposit countable numbers of quantum dots on both flat and structured substrates with a few nanometer precision. We also demonstrate that the autofocusing capability of the printing method enables placement of quantum dots preferentially at plasmonic hot spots. We exploit this control and design diffraction-limited photonic and plasmonic sources with arbitrary wavelength, shape, and intensity. We show that simple far-field illumination can excite these near-field sources and generate fundamental plasmonic wave-patterns (plane and spherical waves). The ability to tailor subdiffraction sources of plasmons with quantum dots provides a complementary technique to traditional scattering approaches, offering new capabilities for nanophotonics.

An intrinsic growth instability in isotropic materials leads to quasi-two-dimensional nanoplatelets

Colloidal nanoplatelets - quasi-two-dimensional sheets of semiconductor exhibiting efficient, spectrally pure fluorescence - form when liquid-phase syntheses of spherical quantum dots are modified. Despite intense interest in their properties, the mechanism behind their anisotropic shape and precise atomic-scale thickness remains unclear, and even counterintuitive when their crystal structure is isotropic. One commonly accepted explanation is that nanoclusters nucleate within molecular templates and then fuse. Here, we test this mechanism for zincblende nanoplatelets and show that they form instead due to an intrinsic instability in growth kinetics. We synthesize CdSe and CdS1-xSex nanoplatelets in template- and solvent-free isotropic melts containing only cadmium carboxylate and chalcogen, a finding incompatible with previous explanations. Our model, based on theoretical results showing enhanced growth on narrow surface facets, rationalizes nanoplatelet formation and experimental dependencies on temperature, time, and carboxylate length. Such understanding should lead to improved syntheses, controlled growth on surfaces, and broader libraries of nanoplatelet materials.Colloidal nanoplatelets are atomically flat, quasi-two-dimensional sheets of semiconductor that can exhibit efficient, spectrally pure fluorescence. Despite intense interest in their properties, the mechanism behind their highly anisotropic shape and precise atomic-scale thickness remains unclear, and even counterintuitive for commonly studied nanoplatelets that arise from isotropic crystal structures (such as zincblende CdSe and lead-halide perovskites). Here we show that an intrinsic instability in growth kinetics can lead to such highly anisotropic shapes. By combining experimental results on the synthesis of CdSe nanoplatelets with theory predicting enhanced growth on narrow surface facets, we develop a model that explains nanoplatelet formation as well as observed dependencies on time and temperature. Based on standard concepts of volume, surface, and edge energies, the resulting growth instability criterion can be directly applied to other crystalline materials. Thus, knowledge of this previously unknown mechanism for controlling shape at the nanoscale can lead to broader libraries of quasi-two-dimensional materials.

Individual Template-Stripped Conductive Gold Pyramids for Tip-Enhanced Dielectrophoresis

Gradient fields of optical, magnetic, or electrical origin are widely used for the manipulation of micro- and nanoscale objects. Among various device geometries to generate gradient forces, sharp metallic tips are one of the most effective. Surface roughness and asperities present on traditionally produced tips reduce trapping efficiencies and limit plasmonic applications. Template-stripped, noble metal surfaces and structures have sub-nm roughness and can overcome these limits. We have developed a process using a mix of conductive and dielectric epoxies to mount template-stripped gold pyramids on tungsten wires that can be integrated with a movable stage. When coupled with a transparent indium tin oxide (ITO) electrode, the conductive pyramidal tip functions as a movable three-dimensional dielectrophoretic trap which can be used to manipulate submicrometer-scale particles. We experimentally demonstrate the electrically conductive functionality of the pyramidal tip by dielectrophoretic manipulation of fluorescent beads and concentration of single-walled carbon nanotubes, detected with fluorescent microscopy and Raman spectroscopy.

Printable Nanoscopic Metamaterial Absorbers and Images with Diffraction-Limited Resolution

The fabrication of functional metamaterials with extreme feature resolution finds a host of applications such as the broad area of surface/light interaction. Nonplanar features of such structures can significantly enhance their performance and tunability, but their facile generation remains a challenge. Here, we show that carefully designed out-of-plane nanopillars made of metal-dielectric composites integrated in a metal-dielectric-nanocomposite configuration can absorb broadband light very effectively. We further demonstrate that electrohydrodynamic printing in a rapid nanodripping mode is able to generate precise out-of-plane forests of such composite nanopillars with deposition resolutions at the diffraction limit on flat and nonflat substrates. The nanocomposite nature of the printed material allows the fine-tuning of the overall visible light absorption from complete absorption to complete reflection by simply tuning the pillar height. Almost perfect absorption (∼95%) over the entire visible spectrum is achieved by a nanopillar forest covering only 6% of the printed area. Adjusting the height of individual pillar groups by design, we demonstrate on-demand control of the gray scale of a micrograph with a spatial resolution of 400 nm. These results constitute a significant step forward in ultrahigh resolution facile fabrication of out-of-plane nanostructures, important to a broad palette of light design applications.

Full-Spectrum Flexible Color Printing at the Diffraction Limit

Color printing at the diffraction limit has been recently explored by fabricating nanoscale plasmonic structures with electron beam lithography. However, only a limited color range and constant intensity throughout the structure have been demonstrated. Here we show an alternative, facile approach relying on the direct, open-atmosphere electrohydrodynamic rapid NanoDrip printing of controlled amounts of red, green, and blue (RGB) quantum dots at a resolution of 250 nm. The narrow emission spectrum of the dots allows the coverage of a very broad color space, exceeding standard RGB (sRGB) of modern display devices. We print color gradients of variable intensity, which to date could not be achieved with diffraction-limited resolution. Showcasing the capabilities of the technology, we present a photorealistic printed image of a colorful parrot with a pixel size of 250 nm.

A customizable class of colloidal-quantum-dot spasers and plasmonic amplifiers

Colloidal quantum dots in silver cavities result in a versatile class of laser-like plasmonic devices for on-chip use. Colloidal quantum dots are robust, efficient, and tunable emitters now used in lighting, displays, and lasers. Consequently, when the spaser—a laser-like source of high-intensity, narrow-band surface plasmons—was first proposed, quantum dots were specified as the ideal plasmonic gain medium for overcoming the significant intrinsic losses of plasmons. Many subsequent spasers, however, have required a single material to simultaneously provide gain and define the plasmonic cavity, a design unable to accommodate quantum dots and other colloidal nanomaterials. In addition, these and other designs have been ill suited for integration with other elements in a larger plasmonic circuit, limiting their use. We develop a more open architecture that decouples the gain medium from the cavity, leading to a versatile class of quantum dot–based spasers that allow controlled generation, extraction, and manipulation of plasmons. We first create aberration-corrected plasmonic cavities with high quality factors at desired locations on an ultrasmooth silver substrate. We then incorporate quantum dots into these cavities via electrohydrodynamic printing or drop-casting. Photoexcitation under ambient conditions generates monochromatic plasmons (0.65-nm linewidth at 630 nm, Q ~ 1000) above threshold. This signal is extracted, directed through an integrated amplifier, and focused at a nearby nanoscale tip, generating intense electromagnetic fields. More generally, our device platform can be straightforwardly deployed at different wavelengths, size scales, and geometries on large-area plasmonic chips for fundamental studies and applications.

Pump-Profile Engineering for Spatial- and Spectral-Mode Control in Two-Dimensional Colloidal-Quantum-Dot Spasers

In the initial proposal of the spaser – a source of coherent, intense, and narrow-band surface plasmons – colloidal quantum dots were envisioned as an ideal gain medium for compensation of the significant losses intrinsic to plasmonics. However, many spasers shown to date have required a single material to both serve as a gain medium and define the plasmonic cavity, a design that prevents the use of quantum dots or other colloidal nanomaterials. In addition, these concepts are inherently challenging for integration in a larger plasmonic circuit.