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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

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

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

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

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 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

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

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