Search

We perform laser spectroscopy at liquid helium temperatures (T=2 K) to investigate single dibenzoterrylene (DBT) molecules doped in anthracene crystals of nanoscopic height fabricated by electrohydrodynamic dripping. Using high-resolution fluorescence excitation spectroscopy, we show that zero-phonon lines of single molecules in printed nanocrystals are nearly as narrow as the Fourier-limited transitions observed for the same guest-host system in the bulk. Moreover, the spectral instabilities are comparable to or less than one linewidth. By recording super-resolution images of DBT molecules and varying the polarization of the excitation beam, we determine the dimensions of the printed crystals and the orientation of the crystals' axes. Electrohydrodynamic printing of organic nano and microcrystals paves the way for a series of applications, where controlled positioning of quantum emitters with narrow optical transitions is desirable.

Emerging colloidal quantum dot (cQD) photodetectors currently challenge established state-of-the-art infrared photodetectors in response speed, spectral tunability, simplicity of solution processable fabrication, and integration onto curved or flexible substrates. Hybrid phototransistors based on 2D materials and cQDs, in particular, are promising due to their inherent photogain enabling direct photosignal enhancement. The photogain is sensitive to both, measurement conditions and photodetector geometry. This makes the cross-comparison of devices reported in the literature rather involved. Here, the effect of device length L and width W scaling to subwavelength dimensions (sizes down to 500 nm) on the photoresponse of graphene-PbS cQD phototransistors was experimentally investigated. Photogain and responsivity were found to scale with 1/LW, whereas the photocurrent and specific detectivity were independent of geometrical parameters. The measurements were performed at scaled bias voltage conditions for comparable currents. Contact effects were found to limit the photoresponse for devices with L < 3 {\mu}m. The relation of gate voltage, bias current, light intensity, and frequency on the photoresponse was investigated in detail, and a photogating efficiency to assess the cQD-graphene interface is presented. In particular, the specific detectivity values in the range between 10^8 to 10^9 Jones (wavelength of 1550 nm, frequency 6 Hz, room temperature) were found to be limited by the charge transfer across the photoactive interface., Comment: 16 pages and 4 figures

Heat exchangers are made of metals because of their high heat conductivity and mechanical stability. Metal surfaces are inherently hydrophilic, leading to inefficient filmwise condensation. It is still a challenge to coat these metal surfaces with a durable, robust and thin hydrophobic layer, which is required for efficient dropwise condensation. Here, we report the non-structured and ultrathin (~6 nm) polydimethylsiloxane (PDMS) brushes on copper that sustain high-performing dropwise condensation in high supersaturation. Due to the flexible hydrophobic siloxane polymer chains, the coating has low resistance to drop sliding and excellent chemical stability. The PDMS brushes can sustain dropwise condensation for up to ~8 h during exposure to 111 {\deg}C saturated steam flowing at 3 m/s, with a 5-7 times higher heat transfer coefficient compared to filmwise condensation. The surface is self-cleaning and can reduce bacterial attachment by 99%. This low-cost, facile, fluorine-free, and scalable method is suitable for a great variety of condensation heat transfer applications., Comment: Submitted to ACS Materials and Interfaces

Jumping of coalescing condensate droplets from superhydrophobic surfaces is an interesting phenomenon which yields marked heat transfer enhancement over the more explored gravity-driven droplet removal mode in surface condensation, a phase change process of central interest to applications ranging from energy to water harvesting. However, when condensate microdroplets coalesce, they can also spontaneously propel themselves omnidirectionally on the surface independent of gravity and grow by feeding from droplets they sweep along the way. Here we observe and explain the physics behind this phenomenon of roaming of coalescing condensate microdroplets on solely nanostructured superhydrophobic surfaces, where the microdroplets are orders of magnitude larger than the underlaying surface nanotexture. We quantify and show that it is the inherent asymmetries in droplet adhesion during condensation, arising from the stochastic nature of nucleation within the nanostructures, that generates the tangential momentum driving the roaming motion. Subsequent dewetting during this conversion initiates a vivid roaming and successive coalescence process, preventing condensate flooding of the surface, and enhancing surface renewal. Finally, we show that the more efficient conversion process of roaming from excess surface energy to kinetic energy results in significantly improved heat transfer efficiency over condensate droplet jumping, the mechanism currently understood as maximum.

Rapid and sustained condensate droplet departure from a surface is key towards achieving high heat transfer rates in condensation, a physical process critical to a broad range of industrial and societal applications. Despite progress in enhancing condensation heat transfer through inducing its dropwise mode with hydrophobic materials, sophisticated surface engineering methods that can lead to further enhancement of heat transfer are still highly desirable. Here, by employing a three-dimensional, multiphase computational approach, we present an effective out-of-plane biphilic surface topography, that reveals an unexplored capillarity-driven departure mechanism of condensate droplets. This texture consists of biphilic diverging micro-cavities wherein a matrix of small hydrophilic spots is placed at their bottom, that is, amongst the pyramid-shaped, superhydrophobic micro-textures forming the cavities. We show that an optimal combination of the hydrophilic spots and the angles of the pyramidal structures can achieve high deformational stretching of the droplets, eventually realizing an impressive slingshot-like droplet ejection process from the texture. Such a droplet departure mechanism has the potential to reduce the droplet ejection volume and thus enhance the overall condensation efficiency, compared to coalescence-initiated droplet jumping from other state-of-the-art surfaces. Simulations have shown that optimal pyramid-shaped biphilic micro-structures can provoke droplet self-ejection at low volumes, up to 56% lower compared to superhydrophobic straight pillars, revealing a promising new surface micro-texture design strategy towards enhancing condensation heat transfer efficiency and water harvesting capabilities.

Soft substrates such as polydimethylsiloxane (PDMS) enhance droplet nucleation during the condensation of water vapour, because their deformability inherently reduces the energetic threshold for heterogeneous nucleation relative to rigid substrates. However, this enhanced droplet nucleation is counteracted later in the condensation cycle, when the viscoelastic dissipation inhibits condensate droplet shedding from the substrate. Here, we show that bulk lubricant infusion in the soft substrate is a potential pathway for overcoming this limitation. We demonstrate that even 5% bulk lubricant infusion in PDMS reduces viscoelastic dissipation in the substrate by more than 30 times and more than doubles the droplet nucleation density. We correlate the droplet nucleation and growth rate with the material properties controlled by design, i.e. the fraction and composition of uncrosslinked chains, shear modulus, and viscoelastic dissipation. Through in-situ, microscale condensation on the substrates, we show that the increase in nucleation density and reduction in pre-coalescence droplet growth rate is insensitive to the percentage of lubricant in PDMS. Our results indicate the presence of a lubricant layer on the substrate surface that cloaks the growing condensate droplets. We visualize the cloaking effect and show that lubricant infusion in PDMS significantly increases the rate of cloaking compared to PDMS without any lubricant infusion. Finally, we show that the overall enhanced condensation due to bulk lubricant infusion in PDMS leads to more than 40% increase in dewing on the substrate.

Lubricant-infused surfaces (LIS) are highly efficient in repelling water and constitute a very promising family of materials for condensation processes occurring in a broad range of energy applications. However, the performance of LIS in such processes is limited by the inherent thermal resistance imposed by the thickness of the lubricant and supporting surface structure, as well as by the gradual depletion of the lubricant over time. Here we present a remarkable, ultra-thin (~70 nm) and conductive LIS architecture, obtained by infusing lubricant into a vertically grown graphene nanoscaffold on copper. The ultra-thin nature of the scaffold, combined with the high in-plane thermal conductivity of graphene, drastically minimize earlier limitations, effectively doubling the heat transfer performance compared to a state-of-the-art CuO LIS surface. We show that the effect of the thermal resistance to the heat transfer performance of a LIS surface, although often overlooked, can be so detrimental that a simple nanostructured CuO surface can outperform a CuO LIS surface, despite film condensation on the former. The present vertical graphene LIS is also found to be resistant to lubricant depletion, maintaining stable dropwise condensation for at least ~7 hours with no significant change of advancing contact angle and contact angle hysteresis. The lubricant consumed by the vertical graphene LIS is 52.6% less than the existing state-of-the-art CuO LIS, making also the fabrication process more economical.

Imparting and maintaining surface superhydrophobicity is receiving significant research attention over the last several years, driven by a broad range of important applications and enabled by advancements in materials and surface nanoengineering. Researchers have investigated the effect of temperature on droplet-surface interactions, which poses additional challenges when liquid nucleation manifests itself, due to ensuing condensation into the surface texture that compromises its anti-wetting behavior. Maintaining surface transparency at the same time poses an additional and significant challenge. Often, the solutions proposed are limited by working temperatures or are detrimental to visibility through the surface. Here we introduce a scalable method employing plasmonic photothermal metasurface composites, able to harvest sunlight and naturally heat the surface, sustaining water repellency and transparency under challenging environmental conditions where condensation and fogging would otherwise be strongly promoted. We demonstrate that these surfaces, when illuminated by sunlight, can prevent impalement of impacting water droplets, even when the droplet to surface temperature difference is 50{\deg}C, by suppressing condensate formation within the texture, maintaining transparency. We also show how the same transparent metasurface coating could be combined and work collaboratively with hierarchical micro- and nanorough textures, resulting in simultaneous superior pressure-driven impalement resistance and avoidance of water nucleation and related possible frosting in supercooled conditions. Our work can find a host of applications as a sustainable solution against impacting water on surfaces such as windows, eyewear, and optical components.

Condensation of water on metallic surfaces is critical for multiple energy conversion processes. Enhancement in condensation heat transfer efficiency often requires surface texturing and hydrophobicity, usually achieved through coatings, to maintain dropwise condensation. However, such surface treatments face conflicting challenges of minimal coating thermal resistance, enhanced coating durability and scalable fabrication. Here we present a thin (~ 2 {\mu}m) polytetrafluoroethylene - carbon nanofiber nanocomposite coating which meets these challenges and sustains coalescence-induced jumping droplet condensation for extended periods under highly demanding condensation conditions. Coating durability is achieved through improved substrate adhesion by depositing a sub-micron thick aluminum primer layer. Carbon nanofibers in a polytetrafluoroethylene matrix increase coating thermal conductivity and promote spontaneous surface nano-texturing to achieve superhydrophobicity for condensate microdroplets. The coating material can be deposited through direct spraying, ensuring economical scalability and versatility for a wide range of substrates. We know of no other coating for metallic surfaces that is able to sustain jumping dropwise condensation under shear of steam at 111 degC flowing at ~ 3 m s-1 over the surface for 10 hours and dropwise condensation for an additional 50 hours. Up to ~ 900% improvement in condensation heat transfer coefficient is achieved compared to conventional filmwise condensation.

Many emerging applications in microscale engineering rely on the fabrication of three-dimensional architectures in inorganic materials. Small-scale additive manufacturing (AM) aspires to provide flexible and facile access to these geometries. Yet, the synthesis of device-grade inorganic materials is still a key challenge towards the implementation of AM in microfabrication. Here, we present a comprehensive overview of the microstructural and mechanical properties of metals fabricated by most state-of-the-art AM methods that offer a spatial resolution $\leq$10$\mu$m. Standardized sets of samples were studied by cross-sectional electron microscopy, nanoindentation and microcompression. We show that current microscale AM techniques synthesize metals with a wide range of microstructures and elastic and plastic properties, including materials of dense and crystalline microstructure with excellent mechanical properties that compare well to those of thin-film nanocrystalline materials. The large variation in materials performance can be related to the individual microstructure, which in turn is coupled to the various physico-chemical principles exploited by the different printing methods. The study provides practical guidelines for users of small-scale additive methods and establishes a baseline for the future optimization of the properties of printed metallic objects $-$ a significant step towards the potential establishment of AM techniques in microfabrication.

The ability of mixing colors with remarkable results had long been exclusive to the talents of master painters. By finely combining colors at different amounts on the palette intuitively, they obtain smooth gradients with any given color. Creating such smooth color variations through scattering by the structural patterning of a surface, as opposed to color pigments, has long remained a challenge. Here, we borrow from the painter's approach and demonstrate color mixing generated by an optical metasurface. We propose a single-layer plasmonic color pixel and a method for nanophotonic structural color mixing based on the additive RGB color model. The color pixels consist of plasmonic nanorod arrays that generate vivid primary colors and enable independent control of color brightness without affecting chromaticity, by simply varying geometric in-plane parameters. By interleaving different nanorod arrays, we combine up to three primary colors on a single pixel. Based on this, two and three color mixing is demonstrated, enabling the continuous coverage of a plasmonic RGB color gamut and yielding a palette with a virtually unlimited number of colors. With this multi-resonant color pixel, we show the photorealistic printing of color and monochrome images at the nanoscale, with ultra-smooth transitions in color and brightness. Our color mixing approach can be applied to a broad range of scatterer designs and materials, and has the potential to be used for multi-wavelength color filters and dynamic photorealistic displays., Comment: 33 pages, 15 figures

Surface fogging is a common phenomenon that can have significant and detrimental effects on surface transparency and visibility. It affects the performance in a wide range of applications including windows, windshields, electronic displays, cameras, mirrors, and eyewear. A host of ongoing research is aimed at combating this problem by understanding and developing stable and effective anti-fogging coatings that are capable of handling a wide range of environmental challenges "passively" without consumption of electrical energy. Here we introduce an alternative approach employing sunlight to go beyond state-of-the-art techniques---such as superhydrophilic and superhydrophobic coatings---by rationally engineering solar absorbing metasurfaces that maintain transparency, while upon illumination, induce localized heating to significantly delay the onset of surface fogging or decrease defogging time. For the same environmental conditions, we demonstrate that our metasurfaces are able to reduce defogging time by up to four-fold and under supersaturated conditions inhibit the nucleation of condensate outperforming conventional state-of-the-art approaches in terms of visibility retention. Our research illustrates a durable and environmentally sustainable approach to passive anti-fogging and defogging for transparent surfaces. This work opens up the opportunity for large-scale manufacturing that can be applied to a range of materials, including polymers and other flexible substrates.

Ice nucleation from vapor presents a variety of challenges across a wide range of industries and applications including refrigeration, transportation, and energy generation. However, a rational comprehensive approach to fabricating intrinsically icephobic surfaces for frost formation-both from water condensation (followed by freezing) and in particular from desublimation (direct growth of ice crystals from vapor)-remains elusive. Here, guided by nucleation physics, we investigate the effect of material composition and surface texturing (atomically smooth to nanorough) on the nucleation and growth mechanism of frost for a range of conditions within the sublimation domain (0 C to -55C; partial water vapor pressures 6 to 0.02 mbar). Surprisingly, we observe that on silicon at very cold temperatures-below the homogeneous ice solidification nucleation limit (< -46 C)-desublimation does not become the favorable pathway to frosting. Furthermore we show that surface nanoroughness makes frost formation on silicon more probable. We experimentally demonstrate at temperatures between -48 C and -55 C that nanotexture with radii of curvature within one order of magnitude of the critical radius of nucleation favors frost growth, facilitated by capillary condensation, consistent with Kelvin's Equation. Our findings show that such nanoscale surface morphology imposed by design to impart desired functionalities-such as superhydrophobicity-or from defects, can be highly detrimental for frost icephobicity at low temperatures and water vapor partial pressures (< 0.05 mbar). Our work contributes to the fundamental understanding of heterogeneous phase transitions well within the equilibrium sublimation domain and has implications for applications such as travel, power generation, and refrigeration.

Surface icing affects the safety and performance of numerous processes in technology. Previous studies mostly investigated freezing of individual droplets. The interaction among multiple droplets during freezing is investigated less, especially on nanotextured icephobic surfaces, despite its practical importance as water droplets never appear in isolation, but in groups. Here we show that freezing of a supercooled droplet leads to spontaneous self-heating and induces strong vaporization. The resulting, rapidly propagating vapor front causes immediate cascading freezing of neighboring supercooled droplets upon reaching them. We put forth the explanation that, as the vapor approaches cold neighboring droplets, it can lead to local supersaturation and formation of airborne microscopic ice crystals, which act as freezing nucleation sites. The sequential triggering and propagation of this mechanism results in the rapid freezing of an entire droplet ensemble resulting in ice coverage of the nanotextured surface. Although cascade freezing is observed in a low-pressure environment, it introduces an unexpected pathway of freezing propagation that can be crucial for the performance of rationally designed icephobic surfaces.

Macro-textured superhydrophobic surfaces can reduce droplet-substrate contact times of impacting water droplets, however, surface designs with similar performance for significantly more viscous liquids are missing, despite their importance in nature and technology such as for chemical shielding, food staining repellency, and supercooled (viscous) water droplet removal in anti-icing applications. Here, we introduce a deterministic, controllable and up-scalable method to fabricate superhydrophobic surfaces with a 3D-printed architecture, combining arrays of alternating surface protrusions and indentations. We show a more than threefold contact time reduction of impacting viscous droplets up to a fluid viscosity of 3.7mPa s, which equals 3.7 times the viscosity of water at room temperature, covering the viscosity of many chemicals and supercooled water. Based on the combined consideration of the fluid flow within and the simultaneous droplet dynamics above the texture, we recommend future pathways to rationally architecture such surfaces, all realizable with the methodology presented here., Comment: ACS Appl. Mater. Interfaces, Article ASAP, Publication Date (Web): November 19, 2018

Inhibiting ice accumulation on surfaces is an energy-intensive task and is of significant importance in nature and technology where it has found applications in windshields, automobiles, aviation, renewable energy generation, and infrastructure. Existing methods rely on on-site electrical heat generation, chemicals, or mechanical removal, with drawbacks ranging from financial costs to disruptive technical interventions and environmental incompatibility. Here we focus on applications where surface transparency is desirable and propose metasurfaces with embedded plasmonically enhanced light absorption heating, using ultra-thin hybrid metal-dielectric coatings, as a passive, viable approach for de-icing and anti-icing, in which the sole heat source is renewable solar energy. The balancing of transparency and absorption is achieved with rationally nano-engineered coatings consisting of gold nanoparticle inclusions in a dielectric (titanium dioxide), concentrating broadband absorbed solar energy into a small volume. This causes a > 10 {\deg}C temperature increase with respect to ambient at the air-solid interface, where ice is most likely to form, delaying freezing, reducing ice adhesion, when it occurs, to negligible levels (de-icing) and inhibiting frost formation (anti-icing). Our results illustrate an effective unexplored pathway towards environmentally compatible, solar-energy-driven icephobicity, enabled by respectively tailored plasmonic metasurfaces, with the ability to design the balance of transparency and light absorption.

Ice accumulation hinders the performance of, and poses safety threats for infrastructure both on the ground and in the air. Previously, rationally designed superhydrophobic surfaces have demonstrated some potential as a passive means to mitigate ice accretion; however, further studies on material solutions that reduce impalement and contact time for impacting supercooled droplets and can also repel droplets that freeze during surface contact are urgently needed. Here we demonstrate the collaborative effect of substrate flexibility and surface nanotexture on enhancing both icephobicity and the repellency of viscous droplets. We first investigate the influence of increased viscosity on impalement resistance and droplet-substrate contact time after impact. Then we examine the effect of droplet partial solidification on recoil and simulate more challenging icing conditions by impacting supercooled water droplets onto flexible and rigid surfaces containing ice nucleation promoters. We demonstrate a passive mechanism for shedding partially solidified droplets under conditions where partial solidification occurs much faster than the natural droplet oscillation which does not rely on converting droplet surface energy into kinetic energy. Using an energy-based model, we identify a previously unexplored mechanism whereby the substrate oscillation and velocity govern the rebound process, with low-areal density and moderately stiff substrates acting to efficiently absorb the incoming droplet kinetic energy and rectify it back, allowing droplets to overcome adhesion and gravitational forces, and recoil. This mechanism applies for a range of droplet viscosities, spanning from low to high viscosity fluids and even ice slurries, which do not rebound from rigid superhydrophobic substrates.

High-quality flat optical elements require efficient light deflection to large angles and over a wide wavelength spectrum. Although phase gradient metasurfaces achieve this by continuously adding phase shifts in the range of 0 to 2{\pi} to the electric field with subwavelength-sized scatterers, their performance is limited by the spatial resolution of phase modulation at the interface. Here, we introduce a new class of metasurfaces based on a general formulation, where the phase shifts cover less than the full 0-2{\pi} range, offering significant advantages. More specifically, this approach allows the realization of metasurfaces with more compact and less mutually-interacting scatterers, thus more precise phase modulation, and advances the performance limits of metasurfaces to domains significantly beyond those of the full coverage phase gradient approach. Applying this concept to both plasmonic and dielectric surfaces, we demonstrate large phase gradients resulting in high-numerical-aperture immersion metalenses (NA=1.4) with near diffraction-limited resolution (~0.32{\lambda}) at visible wavelengths. Our concept enables added functionalities such as a broadband performance and wavelength de-multiplexing on a single layer, surpassing the theoretical cross-polarization transmission efficiency limit for single-layer plasmonic metasurfaces, and yields 67% efficiency for dielectric metasurfaces. This work paves the way toward realizing high-resolution flat optical elements and efficient plasmonic metadevices., Comment: 17 pages, 5 figures

Separating petroleum hydrocarbons from water is an important problem to address in order to mitigate the disastrous effects of hydrocarbons on aquatic ecosystems. A rational approach to address the problem of marine oil water separation is to disperse the oil with the aid of surfactants in order to minimize the formation of large slicks at the water surface and to maximize the oil-water interfacial area. Here we investigate the fundamental wetting and transport behavior of such surfactant-stabilized droplets and the flow conditions necessary to perform sieving and separation of these stabilized emulsions. We show that, for water soluble surfactants, such droplets are completely repelled by a range of materials (intrinsically underwater superoleophobic) due to the detergency effect; therefore, there is no need for surface micro/nanotexturing or chemical treatment to repel the oil and prevent fouling of the filter. We then simulate and experimentally investigate the effect of emulsion flow rate on the transport and impact behavior of such droplets on rigid meshes to identify the minimum pore opening (w) necessary to filter a droplet with a given diameter (d) in order to minimize the pressure drop across the mesh and therefore maximize the filtering efficiency, which is strongly dependent on w. We define a range of flow conditions and droplet sizes where minimum droplet deformation is to be expected and therefore find that the condition of is sufficient for efficient separation. With this new understanding, we demonstrate the use of a commercially available filter--without any additional surface engineering or functionalization--to separate oil droplets from a surfactant stabilized emulsion with a flux of 11,000 L m$^{-2}$ hr$^{-1}$ bar$^{-1}$. We believe these findings can inform the design of future oil separation materials.

The controlled handling of liquids and colloidal suspensions as they interact with surfaces, targeting a broad palette of related functionalities, is of great importance in science, technology, and nature. When small liquid volumes need to be processed in microfluidic devices, contamination on the solid-liquid interface and loss of liquid due to adhesion on the transport channels are two very common problems that can significantly alter the process outcome, e.g. the chemical reaction efficiency, or the purity and the final concentrations of a suspension. It is therefore no surprise that both levitation and minimal contact transport methods including non wetting surfaces have been developed to minimize the interactions between liquids and surfaces. Here we demonstrate contactless surface levitation and transport of liquid drops, realized by harnessing and sustaining the natural sublimation of a solid carbon dioxide-coated substrate to generate a continuous supporting vapor layer. The capability and limitations of this technique in handling liquids of extreme surface tension and kinematic viscosity values are investigated both experimentally and theoretically. The sublimating coating is capable of repelling many viscous and low surface tension liquids, colloidal suspensions, and non-Newtonian fluids as well, displaying outstanding omniphobic properties. Finally, we demonstrate how sublimation can be used for liquid transport, mixing and drop coalescence, with a sublimating layer coated on an underlying substrate with prefabricated channels, conferring omniphobicity with a simple physical approach, rather than a chemical one.

A heat exchange interface at subzero temperature in a water vapor environment, exhibits high probability of frost formation due to freezing condensation, a factor that markedly decreases the heat transfer efficacy due to the considerable thermal resistance of ice. Here we report a novel strategy to delay ice nucleation on these types of solid-water vapor interfaces. With a process-driven mechanism, a self-generated liquid intervening layer immiscible to water, is deposited on a textured superhydrophobic surface and acts as a barrier between the water vapor and the solid substrate. This liquid layer imparts remarkable slippery conditions resulting in high mobility of condensing water droplets. A large increase of the ensuing ice coverage time is shown compared to the cases of standard smooth hydrophilic or textured superhydrophobic surfaces. During deicing of these self-impregnating surfaces we show an impressive tendency of ice fragments to skate expediting defrosting. Robustness of such surfaces is also demonstrated by operating them under subcooling for at least 490hr without a marked degradation. This is attributed to the presence of the liquid intervening layer, which protects the substrate from hydrolyzation enhancing longevity and sustaining heat transfer efficiency., Comment: This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Materials & Interfaces, copyright (c) American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see pubs.acs.org/doi/abs/10.1021/acsami.7b00186

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 surface plasmons, was first proposed, quantum dots were specified as the ideal plasmonic gain medium. Subsequent spaser designs, however, have required a single material to simultaneously provide gain and define the plasmonic cavity, an approach ill-suited to quantum dots and other colloidal nanomaterials. Here 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 high-quality-factor, aberration-corrected, Ag plasmonic cavities. We then incorporate quantum dots via electrohydrodynamic printing18,19 or drop-casting. Photoexcitation under ambient conditions generates monochromatic plasmons above threshold. This signal is extracted, directed through an integrated amplifier, and focused at a nearby nanoscale tip, generating intense electromagnetic fields. This spaser platform, deployable at different wavelengths, size scales, and geometries, can enable more complex on-chip plasmonic devices.

Advancing open atmosphere printing technologies to produce features in the nanoscale range has important and broad applications ranging from electronics, to photonics, plasmonics and biology. Recently an electrohydrodynamic printing regime has been demonstrated in a rapid dripping mode (termed NanoDrip), where the ejected colloidal droplets from nozzles of diameters of O(1 {\mu}m) can controllably reach sizes an order of magnitude smaller than the nozzle and can generate planar and out-of-plane structures of similar sizes. Despite demonstrated capabilities, our fundamental understanding of important aspects of the physics of NanoDrip printing needs further improvement. Here we address the topics of charge content and transport in NanoDrip printing. We employ quantum dot and gold nanoparticle dispersions in combination with a specially designed, auxiliary, asymmetric electric field, targeting the understanding of charge locality (particles vs. solvent) and particle distribution in the deposits as indicated by the dried nanoparticle patterns (footprints) on the substrate. We show that droplets of alternating charge can be spatially separated when applying an ac field to the nozzle. The nanoparticles within a droplet are distributed asymmetrically under the influence of the auxiliary lateral electric field, indicating that they are the main carriers. We also show that the ligand length of the nanoparticles in the colloid affects their mobility after deposition (in the sessile droplet state).

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 photo-realistic printed image of a colorful parrot with a pixel size of 250 nm.

The fabrication of functional metamaterials with extreme feature resolution finds a host of applications such as the broad area of surface/light interaction. Non-planar 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 non-flat 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 ultra-high resolution facile fabrication of out-of-plane nanostructures, important to a broad palette of light design applications. nanostructures, important to a broad palette of light design applications.

It is generally accepted that the hydrophilic property of graphene can be affected by the underlying substrate. However, the role of intrinsic vs. substrate contributions and the related mechanisms are vividly debated. Here we show that the intrinsic hydrophilicity of graphene can be intimately connected to the position of its Fermi level, which affects the interaction between graphene and water molecules. The underlying substrate, or dopants, can tune hydrophilicity by modulating the Fermi level of graphene. By shifting the Fermi level of graphene away from its Dirac point, via either chemical or electrical voltage doping, we show enhanced hydrophilicity with experiments and first principle simulations. Increased vapor condensation on graphene, induced by a simple shifting of its Fermi level, exemplifies applications in the area of interfacial transport phenomena., Comment: 18 pages, 5 figures

The fluid dynamics video shows the acoustophoretic handling of a metal sodium chunks and a water droplets before, during and after mixing. The violent exothermal reaction between solid and liquid introduces an additional phase (hydrogen gas). We developed a unique concept for using ultrasound to stably levitated and move along a plane multiple objects in air, independently from their electromagnetic nature and aspect ratio. This contactless material handling can be extended to hazardous, chemical or radioactive samples., Comment: Videos