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With polarized and angle-resolved Raman spectroscopy studies on single two-dimensional layered perovskites (2DLP) flakes with different ammonium molecules as organic cations, in 2020 we revealed the very rich phonon spectra in the low-frequency regime. Although the phonon bands at low frequency can generally be attributed to the vibrations of the inorganic lattice, we found very different phonon spectra for the same lead-bromide octahedra composition by only changing the type of the organic cations. In addition, the intensity of the different phonon modes depended strongly on the angle of the linearly polarized excitation beam with respect to the in-plane axes of the octahedra lattice. In 2022, we mapped this angular dependence of the phonon modes, which enabled to identify the directionality of the different lattice vibrations. By correlating the phonon spectra with the temperature-dependent emission for a set of 2DLPs that featured very different STE emission, we demonstrated that the exciton relaxation cannot be related to coupling with a single (longitudinal optical) phonon band, and that several phonon bands should be involved in the emission process. We performed angle-resolved polarized emission and Raman spectroscopy on the same two-dimensional lead iodide perovskite microcrystals, which revealed the impact of the organic cations on the linear polarization of the emission, and corroborated our interpretation that multiple phonon bands should be involved in the radiative recombination process. Our studies revealed a wealth of highly directional low-frequency phonons in 2DLPs from which several bands are involved in the emission process, which leads to diverse optical and vibrational properties depending on the type of organic cation in the material., Comment: 36 pages, 8 figures and 1 table

Solid-state nanopore gating inspired by biological ion channels is gaining increasing traction due to a large range of applications in biosensing and drug delivery. Integration of stimuli-responsive molecules such as poly(N-isopropylacrylamide) (PNIPAM) inside nanopores can enable temperature-dependent gating, which so far has only been demonstrated using external heaters. In this work, we combine plasmonic resonators inside the nanopore architecture with PNIPAM to enable optical gating of individual or multiple nanopores with micrometer resolution and a switching speed of few milliseconds by thermo-plasmonics. We achieve a temperature change of 40 kelvin per millisecond and demonstrate the efficacy of this method using nanopore ionic conductivity measurements that enables selective activation of individual nanopores in an array. Moreover, the selective gating of specific nanopores in an array can set distinct ionic conductance levels: low, medium, and high (i.e., 0, 1, and 2), which could be exploited for logical gating with optical signal control. Such selective optical gating in nanopore arrays marks a breakthrough in nanofluidics, as it paves the way towards smart devices that offer multifunctional applications including biosensing, targeted drug delivery, and fluidic mixing.

Nanopore sensing is a key technology for single-molecule detection and analysis. Solid-state nanopores have emerged as a versatile platform, since their fabrication allows to engineer their properties by controlling size, shape, and chemical functionalization. However, lithography-based fabrication approaches for non-planar nanopores-on-chip rely on polymers that have limits with respect to hard- and robustness, durability, and refractive index. In this respect, nanopores made of metal oxides with high dielectric constant would be much more favourable and have the potential to extend the suitability of solid-state nanopores towards optoelectronic technologies. Here, we present a versatile method to fabricate three-dimensional nanopores of different dielectric oxides with controlled shapes. Our approach uses photoresist only as a template in the focused-ion-beam lithography to define the nanopore shape, which is subsequently coated with different oxides (SiO2, Al2O3, TiO2 and HfO2) by atomic-layer deposition. Then the photoresist is fully removed by chemo-physical treatment, resulting in nanopores entirely made from dielectric oxides on a thin solid-state membrane. Our methodology allows straightforward fabrication of convex, straight, and concave nanopore shapes that can be employed in various technologies and applications. We explored their performance as ionic nanochannels and investigated the dependence of the ionic current rectification on the nanopore geometry. We found hysteresis in the ionic conductance that enables potential applications of the nanopores in memristors. We also investigated the dielectric oxide nanopores for DNA sensing by measuring both cis-trans and trans-cis translocations and support our data with numerical simulations based on the Poisson-Nernst-Planck model.

Two-dimensional metal-halide perovskites are highly versatile for light-driven applications due to their exceptional variety in material composition, which can be exploited for tunability of mechanical and optoelectronic properties. The band edge emission is defined by structure and composition of both organic and inorganic layers, and electron-phonon coupling plays a crucial role in the recombination dynamics. However, the nature of the electron-phonon coupling and which kind of phonons are involved is still under debate. Here we investigate the emission, reflectance and phonon response from single two-dimensional lead-iodide microcrystals with angle-resolved polarized spectroscopy. We find an intricate dependence of the emission polarization with the vibrational directionality in the materials, which reveals that several bands of the low-frequency phonons with non-orthogonal directionality contribute to the band edge emission. Such complex electron-phonon coupling requires adequate models to predict the thermal broadening of the emission and provides opportunities to design its polarization properties., Comment: 22 pages, 4 figures

There is a high current interest for novel plasmonic platforms and materials able to extend their applicability into the ultraviolet (UV) region of the electromagnetic spectrum. In the UV it is possible to explore spectral properties of biomolecules with small cross section in the visible spectral range. However, most used metals in plasmonics have their resonances at wavelengths > 350 nm. Aluminum and rhodium are two interesting candidate materials for UV plasmonics, and in this work we developed a simple and low-cost preparation of functional substrates based on nanoporous aluminum decorated with rhodium nanoparticles. We demonstrate that these functionalized nanoporous metal films can be exploited as plasmonic materials suitable for enhanced UV Raman spectroscopy

Ionic Current Rectification (ICR) can appear in nanopores, causing a diode-like behavior that originates from different efficiency of ion transport through the pore channel with respect to the applied voltage bias polarity. This effect is particularly interesting for nanopores with a short channel length, that is smaller than 500 nm, because then the dependence of the ion current on the direction along which the ions pass through the channel is determined by the geometry and material of the nanopore, and by the ion concentration in the electrolyte. Surface charges can play an important role, and therefore nanopores consisting of multiple materials can induce ICR because of different charge distributions at the nanopore-electrolyte interface for the different material sections. In this work, we study four solid-state nanopore designs considering different geometries of charge distributions along the inner and outer surfaces of nanopores, and evaluate their impact on ICR with six different electrolytes. The direct comparison between experimental data and modeling enables to understand how the different surface charge configurations impact the ICR.

Nanoporous metals are a class of nanostructured materials finding extensive applications in multiple fields thanks to their unique properties attributed to their high surface area and interconnected nanoscale ligaments. They can be pre-pared following different strategies, but the deposition of an arbitrary pure porous metal is still challenging. Recently, a dry synthesis of nanoporous films based on the plasma treat-ment of metal thin layers deposited by physical vapour deposition has been demonstrated, as a general route to form pure nanoporous films from a large set of metals. An interest-ing aspect related to this approach is the possibility to apply the same methodology to deposit the porous films as a multilayer. In this way, it is possible to explore the properties of different porous metals in close contact. As demonstrated in this paper, interesting plasmonic properties emerge in a nanoporous Au-Ag bi-layer. The versatility of the method coupled with the possibility to include many different metals, provides an opportunity to tailor their optical resonances and to exploit the chemical and mechanical properties of compo-nents, which is of great interest to applications ranging from sensing, to photochemistry and photocatalysis.

The field of plasmonics is capable of enabling interesting applications in the different wavelength ranges, spanning from the ultraviolet up to the infrared. The choice of plasmonic material and how the material is nanostructured have significant implications for ultimate performance of any plasmonic device. Artificially designed nanoporous metals have interesting material properties including large specific surface area, distinctive optical properties, high electrical conductivity, and reduced stiffness, implying their potentials for many applications. This manuscript reviews the wide range of available nanoporous metals, mainly focusing on their properties as plasmonic materials. While extensive reports on the use and characterization of NPMs exist, a detailed discussion on their connection with surface plasmons and enhanced spectroscopies as well as photocatalysis is missing. Here, we report on different metals investigated, from the most used nanoporous gold to mixed metal compounds, and discuss each of these plasmonic materials suitability for a range of structural design and applications. Finally, we discuss the potentials and limitations of the traditional and alternative plasmonic materials for applications in enhanced spectroscopy and photocatalysis.

We show that plasmonic solid-state nanopores with tunable hole diameter can be prepared via a photocatalytic effect resulting from the enhanced electromagnetic field inside a metallic ring prepared on top of a dielectric nanotube. Under white light illumination, the maximum field intensity in these nanorings induces a site selective metal nucleation and growth. We used this approach to prepare bare Au and bimetallic Au-Ag nanorings and demonstrate the reduction of the initial inner diameter of the nanopore down to 4 nanometers. This process can be applied over large arrays with good reproducibility and good control on the nanopore diameter. The tunability of the nanopore diameter can be used to enable optimized detection of single entities with different size, such as single nanoparticles or biomolecules. As proof-of-concept, we demonstrate the versatility of the platform to perform single object detection of dsDNA, and Au nanoparticles with a diameter of 15 nm and 30 nm. We support our experimental findings with numerical simulations that provide insights into the electromagnetic field intensity distribution, showing that a field intensity enhancement of up to 104 can be achieved inside the nanopores. This strong field confinement inside the final nanopore can be used to perform enhanced optical measurements, and to generate local heating, thereby modifying the ionic conductance of the nanopore

Atomistically detailed computational studies of nanocrystals, such as those derived from the promising lead-halide perovskites, are challenging due to the large number of atoms and lack of symmetries to exploit. Here, focusing on methylammonium lead iodide nanocrystals, we combine a real-space tight binding model with the GW approximation to the self-energy and obtain exciton wavefunctions and absorption spectra via solutions of the associated Bethe-Salpeter equation. We find that the size dependence of carrier confinement, dielectric contrast, electron-hole exchange, and exciton binding energies has a strong impact on the lowest excitation energy, which can be tuned by almost 1 eV over the diameter range of 2-6 nm. Our calculated excitation energies are about 0.2 eV higher than experimentally measured photoluminescence, and they display the same qualitative size dependence. Focusing on the fine structure of the band-edge excitons, we find that the lowest-lying exciton is spectroscopically dark and about 20-30 meV lower in energy than the higher-lying triplet of bright states, whose degeneracy is slightly broken by crystal field effects., Comment: 8 pages, 4 figures

Metamaterials have recently established a new paradigm for enhanced light absorption in state-of-the-art photodetectors. Here, we demonstrate broadband, highly efficient, polarization-insensitive, and gate-tunable photodetection at room temperature in a novel metadevice based on gold/graphene Sierpinski carpet plasmonic fractals. We observed an unprecedented internal quantum efficiency up to 100% from the near-infrared to the visible range with an upper bound of optical detectivity of $10^{11}$ Jones and a gain up to $10^{6}$, which is a fingerprint of multiple hot carriers photogenerated in graphene. Also, we show a 100-fold enhanced photodetection due to highly focused (up to a record factor of $|E/E_{0}|\approx20$ for graphene) electromagnetic fields induced by electrically tunable multimodal plasmons, spatially localized in self-similar fashion on the metasurface. Our findings give direct insight into the physical processes governing graphene plasmonic fractal metamaterials. The proposed structure represents a promising route for the realization of a broadband, compact, and active platform for future optoelectronic devices including multiband bio/chemical and light sensors., Comment: 10 pages, 6 figures

Two-dimensional colloidal halide perovskite nanocrystals are promising materials for light emitting applications. In addition, they can be used as components to create a variety of materials through physical and chemical transformations. Recent studies focused on nanoplatelets that are able to self-assemble and transform on solid substrates. Yet, the mechanism behind the process and the atomic arrangement of their assemblies remain unclear. Here, we present the transformation of self-assembled stacks of CsPbBr$_3$ nanoplatelets in solution, capturing the different stages of the process by keeping the solutions at room temperature and monitoring the nanocrystal morphology over a period of a few months. Using ex-situ transmission electron microscopy and surface analysis, we demonstrate that the transformation mechanism can be understood as oriented attachment, proceeding through the following steps: i) desorption of the ligands from the particles surfaces, causing the merging of nanoplatelet stacks, which first form nanobelts; ii) merging of neighboring nanobelts that form more extended nanoplates; and iii) attachment of nanobelts and nanoplates, which create objects with an atomic structure that resemble a mosaic made of broken nanotiles. We reveal that the starting nanoplatelets merge seamlessly and defect-free on an atomic scale in small and thin nanobelts. However, aged nanobelts and nanoplates, which are mainly stabilized by amine/ammonium ions, link through a bilayer of CsBr. In this case, the atomic columns of neighboring perovskite lattices shift by a half-unit-cell, forming Ruddlesden-Popper planar faults., Comment: 28 pages, 5 Figures

Resistive switching memories allow electrical control of the conductivity of a material, by inducing a high resistance (OFF) or a low resistance (ON) state, using electrochemical and ion transport processes. As alternative to high temperature and vacuum-based physical sulphurization methods of silver (Ag), here we propose, as resistive switching medium, a layer built from colloidal Ag$_{2-x}$S nanocrystals -compatible with solution-processed approaches. The effect of the electrode size (from macro- to micro-scale), composition (Ag, Ti and Pt) and geometry on the device performance together with the electrochemical mechanisms involved are evaluated. We achieved an optimized Ag/Ti bowtie proof-of-concept configuration by e-beam lithography, which fulfils the general requirements for ReRAM devices in terms of low power consumption and reliable $I_{ON}/I_{OFF}$ ratio. This configuration demonstrates reproducible switching between ON and OFF states with data endurance of at least 20 cycles; and an $I_{ON}/I_{OFF}$ ratio up to 10$^3$ at low power consumption (0.1V readout), which outperforms previous results in literature for devices with resistive layers fabricated from silver chalcogenide nanoparticles.

The surface ligands on colloidal nanocrystals (NCs) play an important role in the performance of NCs based optoelectronic devices such as photovoltaic cells, photodetectors and light emitting diodes (LEDs). On one hand, the NC emission depends critically on the passivation of the surface to minimize trap states that can provide non-radiative recombination channels. On the other hand, the electrical properties of NC films are dominated by the ligands that constitute the barriers for charge transport from one NC to its neighbor. Therefore, surface modifications via ligandexchange have been employed to improve the conductance of NC films. However, in light emitting devices, such surface modifications are more critical due to their possible detrimental effects on the emission properties. In this work, we study the role of surface ligand modifications on the optical and electrical properties of CdSe/CdS dot-in-rods (DiRs) in films, and investigate their performance in all-solution processed LEDs. The DiR films maintain high PLQY, around 40-50%, and their electroluminescence in the LED preserves the excellent color purity of the PL. In the LEDs, the ligand-exchange boosted the luminance, reaching a four-fold increase from 2200 cd/m2 for native surfactants to 8500 cd/m2 for the exchanged aminoethanethiol ligands. Moreover, the efficiency roll-off, operational stability, and shelf life are significantly improved, and the external quantum efficiency is modestly increased from 5.1 % to 5.4 %. We relate these improvements to the increased conductivity of the emissive layer, and to the better charge balance of the electrically injected carriers. In this respect, we performed ultraviolet photoelectron spectroscopy (UPS) to obtain deeper insight in the band alignment of the LED structure., Comment: 26 pages, 4 figures

Colloidal nanocrystals are a promising fluorescent class of materials, whose spontaneous emission features can be tuned over a broad spectral range via their composition, geometry and size. However, towards embedding nanocrystals films in elaborated device geometries, one significant drawback is the sensitivity of their emission properties on further fabrication processes like lithography, metal or oxide deposition, etc. In this work, we demonstrate how bright emitting and robust thin films can be obtained by combining nanocrystal deposition from solutions via spin2 coating with subsequent atomic layer deposition of alumina. For the resulting composite films, the layer thickness can be controlled on the nanoscale, and their refractive index can be finely tuned by the amount of deposited alumina. Ellipsometry is used to measure the real and imaginary part of the dielectric permittivity, which gives direct access to the wavelength dependent refractive index absorbance of the film. Detailed analysis of the photophysics of thin films of core-shell nanocrystal with different shape and different shell thickness allow to correlate the behavior of the photoluminescence and of the decay life time to the changes in the non-radiative rate that are induced by the alumina deposition. We show that the photoemission properties of such composite films are stable in wavelength and intensity over several months, and that the photoluminescence completely recovers from heating processes up to 240$^\circ$C. The latter is particularly interesting, since it demonstrates robustness to the typical heat treatment that is needed in several process steps like resist-based lithography and deposition by thermal or electron beam evaporation of metals or oxides., Comment: 20 pages, 4 figures, SYNOPSIS TOC

The interaction between excitons and phonons in semiconductor nanocrystals plays a crucial role in the exciton energy spectrum and dynamics, and thus in their optical properties. We investigate the exciton2 phonon coupling in giant-shell CdSe/CdS core-shell nanocrystals via resonant Raman spectroscopy. The Huang-Rhys parameter is evaluated by the intensity ratio of the longitudinal-optical (LO) phonon of CdS with its first multiscattering (2LO) replica. We used four different excitation wavelengths in the range from the onset of the CdS shell absorption to well above the CdS shell band edge to get insight into resonance effects of the CdS LO phonon with high energy excitonic transitions. The isotropic spherical giant-shell nanocrystals show consistently stronger exciton-phonon coupling as compared to the anisotropic rod-shaped dot-in-rod (DiR) architecture, and the 2LO/LO intensity ratio decreases for excitation wavelengths approaching the CdS band edge. The strong exciton-phonon coupling in the spherical giant-shell nanocrystals can be related to the delocalization of the electronic wave functions. Furthermore, we observe the radial breathing modes of the GS nanocrystals and their overtones by ultralow frequency Raman spectroscopy with nonresonant excitation, using laser energies well below the band gap of the heteronanocrystals, and highlight the differences between higher order, Comment: 16 pages, 3 figures

Metal/Insulator/Metal nanocavities (MIMs) are highly versatile systems for nanometric light confinement and waveguiding, and their optical properties are mostly interpreted in terms of surface plasmon polaritons. Although classic electromagnetic theory accurately describes their behavior, it often lacks physical insight, letting some fundamental aspects of light interaction with these structures unexplored. In this work, we elaborate a quantum mechanical description of the MIM cavity as a double barrier quantum well. We identify the square of the imaginary part of the refractive index of the metal as the optical potential, and find that MIM cavity resonances are suppressed if the ratio n/\k{appa} exceeds a certain limit, which shows that low n and high \k{appa} are desired for strong and sharp cavity resonances. Interestingly, the spectral regions of cavity mode suppression correspond to the interband transitions of the metals, where the optical processes are intrinsically non-Hermitian. The quantum treatment allows to describe the tunnel effect for photons, and reveals that the MIM cavity resonances can be excited by resonant tunneling via illumination through the metal, without the need of momentum matching techniques such as prisms or grating couplers. By combining this analysis with spectroscopic ellipsometry on experimental MIM structures, and by developing a simple harmonic oscillator model of the MIM for the calculation of its effective permittivity, we show that the cavity eigenmodes coincide with low-loss zeros of the effective permittivity., Comment: 33 pages, 7 figures

Plasmonic metasurfaces have spawned the field of flat optics using nanostructured planar metallic or dielectric surfaces that can replace bulky optical elements and enhance the capabilities of traditional far-field optics. Furthermore, the potential of flat optics can go far beyond far-field modulation, and can be exploited for functionality in the near-field itself. Here, we design metasurfaces based on aperiodic arrays of plasmonic Au nanostructures for tailoring the optical near-field in the visible and near-infrared spectral range. The basic element of the arrays is a rhomboid that is modulated in size, orientation and position to achieve the desired functionality of the micron-size metasurface structure. Using two-photon-photoluminescence as a tool to probethe near-field profiles in the plane of the metasurfaces, we demonstrate the molding of light into different near-field intensity patterns and active pattern control via the far-field illumination. Finite element method simulations reveal that the near-field modulation occurs via a combination of the plasmonic resonances of the rhomboids and field enhancement in the nanoscale gaps in between the elements. This approach enables optical elements that can switch the near-field distribution across the metasurface via wavelength and polarization of the incident far-field light, and provides pathways for light matter interaction in integrated devices., Comment: 26 pages, 7 figures

The coupling between multiple nanocavities in close vicinity leads to hybridization of their modes. Stacked Metal/Insulator/Metal (MIM) nanocavities constitute a highly versatile and very interesting model system to study and engineer such mode coupling, since they can be realized by lithography-free fabrication methods with fine control on the optical and geometrical parameters. The resonant modes of such MIM cavities are epsilon-near-zero (ENZ) resonances, which are appealing for non-linear photophysics and a variety of applications. Here we study the hybridization of ENZ resonances in MIMIM nanocavities, obtaining a very large mode splitting reaching 0.477 eV, Q factors of the order of 40 in the visible spectral range, and fine control on the resonance wavelength and mode linewidth by tuning the thickness of the dielectric and metallic layers. A semi-classical approach that analyses the MIMIM structure as a double quantum well system allows to derive the exact analytical dispersion relation of the ENZ resonances, achieving perfect agreement with numerical simulations and experiments. Interestingly, the asymmetry of the mode splitting in a symmetric MIMIM cavity is not reflected in the classical model of coupled oscillators, which can be directly related to quantum mechanical tunneling for the coupling of the two cavities. Interpreting the cavity resonances as resonant tunneling modes elucidates that can be excited without momentum matching techniques. The broad tunability of high-quality ENZ resonances together with their strong coupling efficiency makes such MIMIM cavities an ideal platform for exploring light-matter interaction, for example, by integration of quantum emitters in the dielectric layers., Comment: 24 pages, 4 figures

Directing and polarizing the emission of a fluorophore is of fundamental importance in the perspective of novel photonic sources based on emerging nano-emitter technologies. These two tasks are usually accomplished by a sophisticated and demanding structuring of the optical environment in which the emitter is immersed, or by non-trivial chemical engineering of its geometry and/or band structure. In this paper, the wavelength and polarization selective spontaneous emission from a dye-embedded in a Metal/Insulator/Metal (d-MIM) nanocavity is demonstrated. A push-pull chromophore with large Stokes shift is embedded in a MIM cavity whose resonances are tuned with the spectral emission band of the chromophore. Angular and polarization resolved spectroscopy experiments reveal that the radiated field is reshaped according to the angular dispersion of the nanocavity, and that its spectrum manifests two bands with different polarization corresponding to the p- and s-polarized resonances of the cavity. The d-MIM cavities are a highly versatile system for polarization and wavelength division multiplexing applications at the nanoscale, as well as for near-field focused emission and nanolenses., Comment: 18 pages, 4 figures

The photoluminescence (PL), color purity, and stability of lead halide perovskite nanocrystals depend critically on the surface passivation. We present a study on the temperature dependent PL and PL decay dynamics of lead bromide perovskite nanocrystals characterized by different types of A cations, surface ligands, and nanocrystal sizes. Throughout, we observe a single emission peak from cryogenic to ambient temperature. The PL decay dynamics are dominated by the surface passivation, and a post-synthesis ligand exchange with a quaternary ammonium bromide (QAB) results in a more stable passivation over a larger temperature range. The PL intensity is highest from 50K-250K, which indicates that the ligand binding competes with the thermal energy at ambient temperature. Despite the favorable PL dynamics of nanocrystals passivated with QAB ligands (monoexponential PL decay over a large temperature range, increased PL intensity and stability), the surface passivation still needs improvement toward increased emission intensity in nanocrystal films., Comment: 19 pages, 5 figures

The vibrational modes in organic/inorganic layered perovskites are of fundamental importance for their optoelectronic properties. The hierarchical architecture of the Ruddlesden-Popper phase of these materials allows for distinct directionality of the vibrational modes withrespect to the main axes of the pseudocubic lattice in the octahedral plane. Here, we study the directionality of the fundamental phonon modes in single exfoliated Ruddlesden-Popper perovskite flakes with polarized Raman spectroscopy at ultralow-frequencies. A wealth of Raman bands is distinguished in the range from 15-150 cm-1 (2-15 meV), whose features depend on the organic cation species, on temperature, and on the direction of the linear polarization of the incident light. By controlling the angle of the linear polarization of the excitation laser with respect to the in-plane axes of the octahedral layer, we gain detailed information on the symmetry of the vibrational modes. The choice of two different organic moieties, phenethylammonium (PEA) and butylammonium (BA) allows to discern the influence of the linker molecules, evidencing strong anisotropy of the vibrations for the (PEA)2PbBr4 samples. Temperature dependent Raman measurements reveal that the broad phonon bands observed at room temperature consist of a series of sharp modes, and that such mode splitting strongly differs for the different organic moieties and vibrational bands., Comment: 25 pages, 4 figures

We demonstrate patterning of metal surfaces based on lift-off of perovskite nanocrystals that enables the fabrication of nanometer-size features without the use of resist-based nanolithography. The perovskite nanocrystals act as templates for defining the shape of the apertures in metal layers, and we exploit the variety of sizes and shapes that can be controlled in the colloidal synthesis to demonstrate the fabrication of nanoholes, nanogaps and guides with size smaller than the wavelength of light in the visible spectrum. The process can be readily integrated with standard lithography and etching techniques for the creation of more complex structures., Comment: 10 pages, 4 figures

Colloidal core/shell nanocrystals are key materials for optoelectronics, enabling control over essential properties via precise engineering of the shape, thickness, and crystal lattice structure of their shell. Here, we apply the growth protocol for CdS branched nanocrystals on CdSe nanoplatelet seeds and obtain bone-shaped heterostructures with a highly anisotropic shell. Surprisingly, the nanoplatelets withstand the high growth temperature of 350 {\deg}C and we obtain structures with a CdSe nanoplatelet core that is overcoated by a shell of cubic CdS, on top of which tetrahedral CdS structures with hexagonal lattice are formed. These complex core/shell nanocrystals show a bandedge emission around 657 nm with a photoluminescence quantum yield of ca. 42 % in solution, which is also retained in thin films. Interestingly, the nanocrystals manifest simultaneous red and green emission, and the relatively long wavelength of the green emission indicates charge recombination at the cubic/hexagonal interface of the CdS shell. The nanocrystal films show amplified spontaneous emission, random lasing, and distributed feedback lasing when the material is deposited on suitable gratings. Our work stimulates the design and fabrication of more exotic core/shell heterostructures where charge carrier delocalization, dipole moment, and other optical and electrical properties can be engineered., Comment: 26 pages, 6 figures, 1 table

Among the large family of transition metal dichalcogenides (TMDCs), recently ReS2 has stood out due to its nearly layer-independent optoelectronic and physicochemical properties. These are related to its 1T distorted octahedral structure, which leads to strong in-plane anisotropy and the presence of active sites at its surface, which makes ReS2 interesting for applications such as gas sensors and catalysts for H2 production. However, the current fabrication methods for ReS2 use chemical or physical vapor deposition (CVD or PVD) processes that are costly and involve complex and lengthy fabrication procedures, therefore limiting their large-scale production and exploitation. To address this issue, we developed a colloidal synthesis approach, which allows the production of ReS2 to be attained at temperatures below 360 Celsius degrees and with reaction times < 2 h, resulting in a more cost-efficient strategy than the CVD and PVD methods. By combining the solution-based synthesis with surface functionalization strategies, we demonstrate the feasibility of colloidal ReS2 nanosheet films for gas sensing of different toxic gases, moisture and other volatile compounds with highly competitive performance in comparison with devices built with CVD-grown ReS2 and MoS2. In addition, the integration of the ReS2 nanosheet films in assemblies, in which they are deposited on top of networks of carbon nanotubes, allowed us to fabricate electrodes for electrocatalysis for H2 production in both acid and alkaline conditions. Results from proof-of-principle devices show an electrocatalytic overpotential that is competitive with devices based on ReS2 produced by CVD, and even with MoS2, WS2 and MoSe2 electrocatalysts.

Ultrafast control of light-matter interactions constitutes a crucial feature in view of new technological frontiers of information processing. However, conventional optical elements are either static or feature switching speeds that are extremely low with respect to the timescales at which it is possible to control light. Here, we exploit high-quality-factor engineered epsilon-near-zero (ENZ) modes of a metal-insulator-metal nanocavity to realize an all-optical ultrafast modulation of the reflectance of light at a tailored wavelength. Our approach is based on the presence of the two, spectrally separated, ENZ absorption resonances of the cavity. Optical pumping of the system at its high energy ENZ mode leads to a strong red-shift of the low energy mode because of the transient increase of the local dielectric function, which leads to a sub-3-ps control of the reflectance at a specific wavelength with a relative modulation depth approaching 120%.

Plasmonics applications have been extending into the ultraviolet region of the electromagnetic spectrum. Unfortunately the commonly used noble metals have intrinsic optical properties that limit their use above 350 nm. Aluminum is probably the most suitable material for UV plasmonics and in this work we show that nanoporous aluminum can be prepared starting from an alloy of Mg3Al2. The porous metal is obtained by means of a galvanic replacement reaction. Such a nanoporous metal can be exploited to achieve a plasmonic material for enhanced UV Raman spectroscopy and fluorescence. Thanks to the large surface to volume ratio this material represents a powerful platform for promoting interaction between plasmonic substrates and molecules in the UV.

We have fabricated UV-sensitive photodetectors based on colloidal CdS nanocrystals and graphene. The nanocrystals act as a sensitizer layer that improves light harvesting leading to high responsivity of the detector. Despite the slow relaxation of the photogenerated charges in the nanocrystal film, faster processes allowed to detect pulses up to a repetition rate of 2 kHz. We have performed time-resolved analysis of the processes occurring in our hybrid system, and discuss possible photo-induced charge transfer mechanisms., Comment: 11 pages, 5 figures

Core-shell CdSe/CdS nanocrystals are a very promising material for light emitting applications. Their solution-phase synthesis is based on surface-stabilizing ligands that makes them soluble in organic solvents, like toluene or chloroform. However, solubility of these materials in water provides many advantages, such as additional process routes and easier handling. So far, solubilization of CdSe/CdS nanocrystals in water that avoids detrimental effects on the luminescent properties, poses a major challenge. This work demonstrates how core-shell CdSe/CdS quantum dot-in-rods can be transferred into water using a ligand exchange method employing mercaptopropionic acid (MPA). Key to maintaining the light-emitting properties is an enlarged CdS rod diameter, which prevents potential surface defects formed during the ligand exchange from affecting the photophysics of the dot-in-rods. Films made from water-soluble dot-in-rods show amplified spontaneous emission (ASE) with a similar threshold (130 microJ/cm2) as the pristine material (115 microJ/cm2). To demonstrate feasibility for lasing applications, self-assembled micro lasers are fabricated via the coffee-ring effect that display single-mode operation and a very low threshold of around 10 microJ/cm2. The performance of these micro lasers is enhanced by the small size of MPA ligands, enabling a high packing density of the dot-in-rods., Comment: 20 pages, 4 figures, published paper with supporting information

Deterministic fractal antennas are employed to realize multimodal plasmonic devices. Such structures show strongly enhanced localized electromagnetic fields typically in the infrared range with a hierarchical spatial distribution. Realization of engineered fractal antennas operating in the optical regime would enable nanoplasmonic platforms for applications, such as energy harvesting, light sensing, and bio/chemical detection. Here, we introduce a novel plasmonic multiband metamaterial based on the Sierpinski carpet (SC) space-filling fractal, having a tunable and polarization-independent optical response, which exhibits multiple resonances from the visible to mid-infrared range. We investigate gold SCs fabricated by electron-beam lithography on CaF$_{2}$ and Si/SiO$_{2}$ substrates. Furthermore, we demonstrate that such resonances originate from diffraction-mediated localized surface plasmons, which can be tailored in deterministic fashion by tuning the shape, size, and position of the fractal elements. Moreover, our findings illustrate that SCs with high order of complexity present a strong and hierarchically distributed electromagnetic near-field of the plasmonic modes. Therefore, engineered plasmonic SCs provide an efficient strategy for the realization of compact active devices with a strong and broadband spectral response in the visible/mid-infrared range. We take advantage of such a technology by carrying out surface enhanced Raman spectroscopy (SERS) on Brilliant Cresyl Blue molecules deposited onto plasmonic SCs. We achieve a broadband SERS enhancement factor up to $10^{4}$, thereby providing a proof-of-concept application for chemical diagnostics., Comment: 14 pages, 6 figures

We present a simple device architecture that allows all-electrical detection of plasmons in a graphene waveguide. The key principle of our electrical plasmon detection scheme is the non-linear nature of the hydrodynamic equations of motion that describe transport in graphene at room temperature and in a wide range of carrier densities. These non-linearities yield a dc voltage in response to the oscillating field of a propagating plasmon. For illustrative purposes, we calculate the dc voltage arising from the propagation of the lowest-energy modes in a fully analytical fashion. Our device architecture for all-electrical plasmon detection paves the way for the integration of graphene plasmonic waveguides in electronic circuits., Comment: 9 pages, 3 figures

CdSe-Au networks were synthesized by a colloidal chemistry technique. They entail CdSe nanorods with a diameter of ~10 nm and a length of ~40 nm, which are joined together by Au domains (~5 nm). Individual networks were positioned by AC dielectrophoresis between bow-tie electrodes with a gap of ~100 nm and their conductivity as well as the photoelectrical properties were investigated. Nanorod networks, with multiple Au domains on the nanorod surface, displayed stable conductivity that was not sensitive to blue laser light illumination. Such nanostructures were transformed by thermal annealing to networks with Au domains only at the nanorod tips. In this system the overall conductivity was reduced, but a clear photocurrent signal could be detected, manifesting semiconductor behavior.

We deposit droplets of nanorods dispersed in solvents on substrate surfaces and let the solvent evaporate. We find that strong contact line pinning leads to dense nanorod deposition inside coffee stain fringes, where we observe large-scale lateral ordering of the nanorods with the long axis of the rods oriented parallel to the contact line. We observe birefringence of these coffee stain fringes by polarized microscopy and we find the direction of the extraordinary refractive index parallel to the long axis of the nanorods., Comment: 11 pages, 6 figures and supporting information

Nano-size objects like metal clusters present an ideal system for the study of quantum phenomena and for constructing practical quantum devices. Integrating these small objects in a macroscopic circuit is, however, a difficult task. So far the nanoparticles have been contacted and addressed by highly sophisticated techniques which are not suitable for large scale integration in macroscopic circuits. We present an optical lithography method that allows for the fabrication of a network of electrodes which are separated by gaps of controlled nanometer size. The main idea is to control the gap size with subnanometer precision using a structure grown by molecular beam epitaxy., Comment: 4 pages, 3 figures

We explore the structural changes in charge the density and the electron configuration of quantum dots caused by the presence of other dots in an array, and the interaction of neighboring dots. We discuss what recent measurements and calculation of the far-infrared absorption reveal about almost isolated quantum dots and investigate some aspects of the complex transition from isolated dots to dots with strongly overlapping electron density. We also address the the effects on the magnetization of such dot array., Comment: 29 papes, 17 included figures. This article is slated to appear as a chapter in "Nano-Physics and Bio-Electronics", edited by T. Chakraborty, F. Peeters, and U. Sivan (to be published by Elsevier Co.)

We have investigated the far-infrared response of quantum dots in modulation doped GaAs heterostructures. We observe novel modes at frequencies below the center-of-mass Kohn mode. Comparison with Hartree-RPA calculations show that these modes arise from the flattened potential in our field-effect confined quantum dots. They reflect pronounced relative motion of the charge density with respect to the center-of-mass., Comment: 8 pages, LaTeX with integrated 6 PostScript figures