Trends in hot carrier distribution for disordered noble-transition metal alloys.

We developed and tested an approach for predicting trends for efficient hot carrier generation among disordered metal alloys. We provide a simple argument for the importance of indirect transitions in the presence of disorder, thus justifying the use of joint density of states (JDOS)-like quantities for exploring these trends. We introduce a newJDOS-like quantity,JDOSK, which heuristically accounts for longer lifetimes of quasiparticles close to the Fermi energy. To demonstrate the efficacy of this new quantity, we apply it to the study of Cu50X50where X = Ag, Au, Pd and Y50Pd50where Y = Au, Ni. We predict that Ni50Pd50produces the most hot carriers among the alloys considered. The improvement in the density of excited photocarriers over the base alloy used, Cu50Ag50, is 3.4 times for 800 nm and 19 times for 1550 nm light. This boost in hot-carrier generation is consequence of the ferromagnetic nature of the Ni alloy. We argue that our method allows efficient material-specific predictions for low bias photoconductivity of alloys.

Efficient Chemical-Free Degradation of Waterborne Micropollutants with an Immobilized Dual-Porous TiO2 Photocatalyst.

Photocatalytic advanced oxidation processes (AOPs) promise a chemical-free route to energy-efficient degradation of waterborne micropollutants if long-standing mass transfer and light management issues can be overcome. Herein, we developed a dual-porous photocatalytic system consisting of a mesoporous (i.e., 2-50 nm pores) TiO2 (P25) photocatalyst supported on macroporous (i.e., >50 nm pores) fused quartz fibers (P25/QF). Our reusable photocatalytic AOP reduces chemical consumption and exhibits excellent energy efficiency, demonstrated by degrading various pharmaceutical compounds (acetaminophen, sulfamethoxazole, and carbamazepine) in natural waters with electrical energy per order (EEO) values of 4.07, 0.96, and 1.35 kWh/m3, respectively. Compared to the conventional H2O2/UVC AOP, our photocatalytic AOP can treat water without chemical additives while reducing energy consumption by over 2800%. We examine these improvements based on mass transport and optical (UVA and UVC) transmittance and demonstrate that the enhancements scale with increasing flow rate.

Monodisperse Sub-100 nm Au Nanoshells for Low-Fluence Deep-Tissue Photoacoustic Imaging.

Nanoparticles with high absorption cross sections will advance therapeutic and bioimaging nanomedicine technologies. While Au nanoshells have shown great promise in nanomedicine, state-of-the-art synthesis methods result in scattering-dominant particles, mitigating their efficacy in absorption-based techniques that leverage the photothermal effect, such as photoacoustic (PA) imaging. We introduce a highly reproducible synthesis route to monodisperse sub-100 nm Au nanoshells with an absorption-dominant optical response. Au nanoshells with 48 nm SiO2 cores and 7 nm Au shells show a 14-fold increase in their volumetric absorption coefficient compared to commercial Au nanoshells with dimensions commonly used in nanomedicine. PA imaging with Au nanoshell contrast agents showed a 50% improvement in imaging depth for sub-100 nm Au nanoshells compared with the smallest commercially available nanoshells in a turbid phantom. Furthermore, the high PA signal at low fluences, enabled by sub-100 nm nanoshells, will aid the deployment of low-cost, low-fluence light-emitting diodes for PA imaging.

Emergent properties from CuPd alloy films under near-infrared excitation.

Noble-transition metal alloys offer emergent optical and electronic properties for near-infrared (NIR) optoelectronic devices. We investigate the optical and electronic properties of CuxPd1-x alloy thin films and their ultrafast electron dynamics under NIR excitation. Ultraviolet photoelectron spectroscopy measurements supported by density functional theory calculations show strong d-band hybridization between the Cu 3d and Pd 4d bands. These hybridization effects result in emergent optical properties, most apparent in the dilute Pd case. Time-resolved terahertz spectroscopy with NIR (e.g., 1550 nm) excitation displays composition-tunable electron dynamics. We posit that the negative peak in the normalized increment of transmissivity (ΔT/T) below 2 ps from dilute Pd alloys is due to non-thermalized hot-carrier generation. On the other hand, Pd-rich alloys exhibit an increase in ΔT/T due to thermalization effects upon ultrafast NIR photoexcitation. CuxPd1-x alloys in the dilute Pd regime may be a promising material for future ultrafast NIR optoelectronic devices.

Resonant Plasmonic-Biomolecular Chiral Interactions in the Far-Ultraviolet: Enantiomeric Discrimination of sub-10 nm Amino Acid Films.

Resonant plasmonic-molecular chiral interactions are a promising route to enhanced biosensing. However, biomolecular optical activity primarily exists in the far-ultraviolet regime, posing significant challenges for spectral overlap with current nano-optical platforms. We demonstrate experimentally and computationally the enhanced chiral sensing of a resonant plasmonic-biomolecular system operating in the far-UV. We develop a full-wave model of biomolecular films on Al gammadion arrays using experimentally derived chirality parameters. Our calculations show that detectable enhancements in the chiroptical signals from small amounts of biomolecules are possible only when tight spectral overlap exists between the plasmonic and biomolecular chiral responses. We support this conclusion experimentally by using Al gammadion arrays to enantiomerically discriminate ultrathin (<10 nm thick) films of tyrosine. Notably, the chiroptical signals of the bare films were within instrumental noise. Our results demonstrate the importance of using far-UV active metasurfaces for enhancing natural optical activity.

Printed Electrode for Measuring Phosphate in Environmental Water.

Phosphate is a major nonpoint source pollutant in both the Louisiana local streams as well as in the Gulf of Mexico coastal waters. Phosphates from agricultural run-off have contributed to the eutrophication of global surface waters. Phosphate environmental dissemination and eutrophication problems are not yet well understood. Thus, this study aimed to monitor phosphate in the local watershed to help identify potential hot spots in the local community (Mississippi River, Louisiana) that may contribute to nutrient loading downstream (in the Gulf of Mexico). An electrochemical method using a physical vapor deposited cobalt microelectrode was utilized for phosphate detection using cyclic voltammetry and amperometry. The testing results were utilized to evaluate the phosphate distribution in river water and characterize the performance of the microsensor. Various characterizations, including the limit of detection, sensitivity, and reliability, were conducted by measuring the effect of interferences, including dissolved oxygen, pH, and common ions. The electrochemical sensor performance was validated by comparing the results with the standard colorimetry phosphate detection method. X-ray photoelectron spectroscopy (XPS) measurements were performed to understand the phosphate sensing mechanism on the cobalt electrode. This proof-of-concept sensor chip could be utilized for on-field monitoring using a portable, hand-held potentiostat.

Synthesis of luminescent core/shell α-Zn3P2/ZnS quantum dots.

Metal chalcogenide nanoparticles offer vast control over their optoelectronic properties via size, shape, composition, and morphology which has led to their use across fields including optoelectronics, energy storage, and catalysis. While cadmium and lead-based nanocrystals are prevalent in applications, concerns over their toxicity have motivated researchers to explore alternate classes of nanomaterials based on environmentally benign metals such as zinc and tin. The goal of this research is to identify material systems that offer comparable performance to existing metal chalcogenide systems from abundant, recyclable, and environmentally benign materials. With band gaps that span the visible through the infrared, II-V direct band gap semiconductors such as tetragonal zinc phosphide (α-Zn3P2) are promising candidates for optoelectronics. To date, syntheses of α-Zn3P2 nanoparticles have been hindered because of the toxicity of zinc and phosphorus precursors, surface oxidation, and defect states leading to carrier trapping and low photoluminescence quantum yield. This work reports a colloidal synthesis of quantum confined α-Zn3P2 nanoparticles from common phosphorus precursor tris(trimethylsilyl)phosphine and environmentally benign zinc carboxylates. Shelling of the nanoparticles with zinc sulfide is shown as a method of preventing oxidation and improving the optical properties of the nanoparticles. These results show a route to stabilizing α-Zn3P2 nanoparticles for optoelectronic device applications.

A Noble-Transition Alloy Excels at Hot-Carrier Generation in the Near Infrared.

Above-equilibrium "hot"-carrier generation in metals is a promising route to convert photons into electrical charge for efficient near-infrared optoelectronics. However, metals that offer both hot-carrier generation in the near-infrared and sufficient carrier lifetimes remain elusive. Alloys can offer emergent properties and new design strategies compared to pure metals. Here, it is shown that a noble-transition alloy, Aux Pd1- x , outperforms its constituent metals concerning generation and lifetime of hot carriers when excited in the near-infrared. At optical fiber wavelengths (e.g., 1550 nm), Au50 Pd50 provides a 20-fold increase in the number of ≈0.8 eV hot holes, compared to Au, and a threefold increase in the carrier lifetime, compared to Pd. The discovery that noble-transition alloys can excel at hot-carrier generation reveals a new material platform for near-infrared optoelectronic devices.

Critical Coupling of Visible Light Extends Hot-Electron Lifetimes for H2O2 Synthesis.

Devices driven by above-equilibrium "hot" electrons are appealing for photocatalytic technologies, such as in situ H2O2 synthesis, but currently suffer from low (<1%) overall quantum efficiencies. Gold nanostructures excited by visible light generate hot electrons that can inject into a neighboring semiconductor to drive electrochemical reactions. Here, we designed and studied a metal-insulator-metal (MIM) structure of Au nanoparticles on a ZnO/TiO2/Al film stack, deposited through room-temperature, lithography-free methods. Light absorption, electron injection efficiency, and photocatalytic yield in this device are superior in comparison to the same stack without Al. Our device absorbs >60% of light at the Au localized surface plasmon resonance (LSPR) peak near 530 nm-a 5-fold enhancement in Au absorption due to critical coupling to an Al film. Furthermore, we show through ultrafast pump-probe spectroscopy that the Al-coupled samples exhibit a nearly 5-fold improvement in hot-electron injection efficiency as compared to a non-Al device, with the hot-electron lifetimes extending to >2 ps in devices photoexcited with fluence of 0.1 mJ cm-2. The use of an Al film also enhances the photocatalytic yield of H2O2 more than 3-fold in a visible-light-driven reactor. Altogether, we show that the critical coupling of Al films to Au nanoparticles is a low-cost, lithography-free method for improving visible-light capture, extending hot-carrier lifetimes, and ultimately increasing the rate of in situ H2O2 generation.

Correlation of circular differential optical absorption with geometric chirality in plasmonic meta-atoms.

We report a strong correlation between the calculated broadband circular differential optical absorption (CDOA) and the geometric chirality of plasmonic meta-atoms with two-dimensional chirality. We investigate this correlation using three common gold meta-atom geometries: L-shapes, triangles, and nanorod dimers, over a broad range of geometric parameters. We show that this correlation holds for both contiguous plasmonic meta-atoms and non-contiguous structures which support plasmonic coupling effects. A potential application for this correlation is the rapid optimization of plasmonic nanostructure for maximum broadband CDOA.

Room-Temperature Strong Coupling of CdSe Nanoplatelets and Plasmonic Hole Arrays.

Exciton polaritons are hybrid light-matter quasiparticles that can serve as coherent light sources. Motivated by applications, room-temperature realization of polaritons requires narrow, excitonic transitions with large transition dipoles. Such transitions must then be strongly coupled to an electromagnetic mode confined in a small volume. While much work has explored polaritons in organic materials, semiconductor nanocrystals present an alternative excitonic system with enhanced photostability and spectral tunability. In particular, quasi-two-dimensional nanocrystals known as nanoplatelets (NPLs) exhibit intense, spectrally narrow excitonic transitions useful for polariton formation. Here, we place CdSe NPLs on silver hole arrays to demonstrate exciton-plasmon polaritons at room temperature. Angle-resolved reflection spectra reveal Rabi splittings up to 149 meV for the polariton states. We observe bright, polarized emission arising from the lowest polariton state. Furthermore, we assess the dependence of the Rabi splitting on the hole-array pitch and the number N of NPLs. While the pitch determines the in-plane momentum for which strong coupling is observed, it does not affect the size of the splitting. The Rabi splitting first increases with NPL film thickness before eventually saturating. Instead of the commonly used [Formula: see text] dependence, we develop an analytical expression that includes the transverse confinement of the plasmon modes to describe the measured Rabi splitting as a function of NPL film thickness.

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

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.

Direct Patterning of Colloidal Quantum-Dot Thin Films for Enhanced and Spectrally Selective Out-Coupling of Emission.

We report on a template-stripping method for the direct surface patterning of colloidal quantum-dot thin films to produce highly luminescent structures with feature sizes less than 100 nm. Through the careful design of high quality bull's-eye gratings we can produce strong directional beaming (10° divergence) with up to 6-fold out-coupling enhancement of spontaneous emission in the surface-normal direction. A transition to narrow single-mode lasing is observed in these same structures at thresholds as low as 120 µJ/cm2. In addition, we demonstrate that these structures can be fabricated on flexible substrates. Finally, making use of the size-tunable character of colloidal quantum dots, we demonstrate spectrally selective out-coupling of light from mixed quantum-dot films. Our results provide a straightforward route toward significantly improved optical properties of colloidal quantum-dot assemblies.

Ultraviolet Plasmonic Chirality from Colloidal Aluminum Nanoparticles Exhibiting Charge-Selective Protein Detection.

Chiral aluminum nanoparticles, dispersed in water, are prepared, which provide strong ultraviolet plasmonic circular dichroism, high-energy superchiral near-fields, and charge-selective protein detection.

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 ~0.004λvac(3) 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.

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.

Complex chiral colloids and surfaces via high-index off-cut silicon.

Silicon wafers are commonly etched in potassium hydroxide solutions to form highly symmetric surface structures. These arise when slow-etching {111} atomic planes are exposed on standard low-index surfaces. However, the ability of nonstandard high-index wafers to provide more complex structures by tilting the {111} planes has not been fully appreciated. We demonstrate the power of this approach by creating chiral surface structures and nanoparticles of a specific handedness from gold. When the nanoparticles are dispersed in liquids, gold colloids exhibiting record molar circular dichroism (>5 × 10(9) M(-1) cm(-1)) at red wavelengths are obtained. The nanoparticles also present chiral pockets for binding.

Fabrication of smooth patterned structures of refractory metals, semiconductors, and oxides via template stripping.

The template-stripping method can yield smooth patterned films without surface contamination. However, the process is typically limited to coinage metals such as silver and gold because other materials cannot be readily stripped from silicon templates due to strong adhesion. Herein, we report a more general template-stripping method that is applicable to a larger variety of materials, including refractory metals, semiconductors, and oxides. To address the adhesion issue, we introduce a thin gold layer between the template and the deposited materials. After peeling off the combined film from the template, the gold layer can be selectively removed via wet etching to reveal a smooth patterned structure of the desired material. Further, we demonstrate template-stripped multilayer structures that have potential applications for photovoltaics and solar absorbers. An entire patterned device, which can include a transparent conductor, semiconductor absorber, and back contact, can be fabricated. Since our approach can also produce many copies of the patterned structure with high fidelity by reusing the template, a low-cost and high-throughput process in micro- and nanofabrication is provided that is useful for electronics, plasmonics, and nanophotonics.

Engineering metallic nanostructures for plasmonics and nanophotonics.

Metallic nanostructures now play an important role in many applications. In particular, for the emerging fields of plasmonics and nanophotonics, the ability to engineer metals on nanometric scales allows the development of new devices and the study of exciting physics. This review focuses on top-down nanofabrication techniques for engineering metallic nanostructures, along with computational and experimental characterization techniques. A variety of current and emerging applications are also covered.

Chemical bath deposition of ZnO nanowires at near-neutral pH conditions without hexamethylenetetramine (HMTA): understanding the role of HMTA in ZnO nanowire growth.

Chemical bath deposition (CBD) is an inexpensive and reproducible method for depositing ZnO nanowire arrays over large areas. The aqueous Zn(NO(3))(2)-hexamethylenetetramine (HMTA) chemistry is one of the most common CBD chemistries for ZnO nanowire synthesis, but some details of the reaction mechanism are still not well-understood. Here, we report the use of in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy to study HMTA adsorption from aqueous solutions onto ZnO nanoparticle films and show that HMTA does not adsorb on ZnO. This result refutes earlier claims that the anisotropic morphology arises from HMTA adsorbing onto and capping the ZnO {10 1 0} faces. We conclude that the role of HMTA in the CBD of ZnO nanowires is only to control the saturation index of ZnO. Furthermore, we demonstrate the first deposition of ZnO nanowire arrays at 90 °C and near-neutral pH conditions without HMTA. Nanowires were grown using the pH buffer 2-(N-morpholino)ethanesulfonic acid (MES) and continuous titratation with KOH to maintain the same pH conditions where growth with HMTA occurs. This semi-batch synthetic method opens many new opportunities to tailor the ZnO morphology and properties by independently controlling temperature and pH.