Degenerately doped metal oxide nanocrystals for infrared light harvesting: insight into their plasmonic properties and future perspectives.

The tuneability of the localized surface plasmon resonance (LSPR) of degenerately doped metal oxide (MOX) nanocrystals (NCs) over a wide range of the infrared (IR) region by controlling NC size and doping content offers a unique opportunity to develop a future generation of optoelectronic and photonic devices like IR photodetectors and sensors. The central aim of this review article is to highlight the distinctive and remarkable plasmonic properties of degenerately or heavily doped MOX nanocrystals by reviewing the comprehensive literature reported so far. In particular, the literature of each MOX NC, i.e. ZnO, CdO, In2O3, and WO3 doped with different dopants, is discussed separately. In addition to discussion of the most commonly used colloidal synthesis approaches, the ultrafast dynamics of charge carriers in NCs and the extraction of LSPR-assisted hot-carriers are also discussed in detail. Finally, future prospective applications of MOX NCs in IR photodetectors and photovoltaic (PV) self-powered chemical sensors are also presented.

Time-domain observation of interlayer exciton formation and thermalization in a MoSe2/WSe2 heterostructure.

Vertical heterostructures of transition metal dichalcogenides (TMDs) host interlayer excitons with electrons and holes residing in different layers. With respect to their intralayer counterparts, interlayer excitons feature longer lifetimes and diffusion lengths, paving the way for room temperature excitonic optoelectronic devices. The interlayer exciton formation process and its underlying physical mechanisms are largely unexplored. Here we use ultrafast transient absorption spectroscopy with a broadband white-light probe to simultaneously resolve interlayer charge transfer and interlayer exciton formation dynamics in a MoSe2/WSe2 heterostructure. We observe an interlayer exciton formation timescale nearly an order of magnitude (~1 ps) longer than the interlayer charge transfer time (~100 fs). Microscopic calculations attribute this relative delay to an interplay of a phonon-assisted interlayer exciton cascade and thermalization, and excitonic wave-function overlap. Our results may explain the efficient photocurrent generation observed in optoelectronic devices based on TMD heterostructures, as the interlayer excitons are able to dissociate during thermalization.

Tamm Plasmon Resonance as Optical Fingerprint of Silver/Bacteria Interaction.

The incorporation of responsive elements into photonic crystals is an effective strategy for fabricating active optical components to be used as sensors, actuators, and modulators. In particular, the combination of simple multilayered dielectric mirrors with optically responsive plasmonic materials has proven to be successful. Recently, Tamm plasmon (TP) modes have emerged as powerful tools for these purposes. These modes arise at the interface between a distributed Bragg reflector (DBR) and a plasmonic layer and can be excited at a normal incidence angle. Although the TP field is located usually at the DBR/metal interface, recent studies have demonstrated that nanoscale corrugation of the metal layer permits access to the TP mode from outside, thus opening exciting perspectives for many real-life applications. In this study, we show that the TP resonance obtained by capping a DBR with a nanostructured layer of silver is responsive to Escherichia coli. Our data indicate that the modification of the TP mode originates from the well-known capability of silver to interact with bacteria, within a process in which the release of Ag+ ions leaves an excess of negative charge in the metal lattice. Finally, we exploited this effect to devise a case study in which we optically differentiated between the presence of proliferative and nonproliferative bacteria using the TP resonance as a read-out. These findings make these devices promising all-optical probes for bacterial metabolic activity, including their response to external stressors.

Recent Progress in Solution Processed Aluminum and co-Doped ZnO for Transparent Conductive Oxide Applications.

With the continuous growth in the optoelectronic industry, the demand for novel and highly efficient materials is also growing. Specifically, the demand for the key component of several optoelectronic devices, i.e., transparent conducting oxides (TCOs), is receiving significant attention. The major reason behind this is the dependence of the current technology on only one material-indium tin oxide (ITO). Even though ITO still remains a highly efficient material, its high cost and the worldwide scarcity of indium creates an urgency for finding an alternative. In this regard, doped zinc oxide (ZnO), in particular, solution-processed aluminum doped ZnO (AZO), is emerging as a leading candidate to replace ITO due to its high abundant and exceptional physical/chemical properties. In this mini review, recent progress in the development of solution-processed AZO is presented. Beside the systematic review of the literature, the solution processable approaches used to synthesize AZO and the effect of aluminum doping content on the functional properties of AZO are also discussed. Moreover, the co-doping strategy (doping of aluminum with other elements) used to further improve the properties of AZO is also discussed and reviewed in this article.

Synthesis of Bioctacene-Incorporated Nanographene with Near-Infrared Chiroptical Properties.

We report the synthesis of a hexabenzoperihexacene (HBPH) with two incorporated octacene substructures, which was unambiguously characterized by single-crystal X-ray analysis. The theoretical isomerization barrier of the (P,P)-/(P,M)-forms was estimated to be 38.4 kcal mol-1 , and resolution was achieved by chiral HPLC. Notably, the enantiomers exhibited opposite circular dichroism responses up to the near-infrared (NIR) region (830 nm) with a high gabs value of 0.017 at 616 nm. Moreover, HBPH demonstrated NIR emission with a maximum at 798 nm and an absolute PLQY of 41 %. The excited-state photophysical properties of HBPH were investigated by ultrafast transient absorption spectroscopy, revealing an intriguing feature that was attributed to the rotational and/or conformational dynamics of HBPH after excitation. These results provide new insight into the design of chiral nanographene with NIR optical properties for potential chiroptical applications.

Zigzag-Edged Polycyclic Aromatic Hydrocarbons from Benzo[m]tetraphene Precursors.

A series of zigzag-edged polycyclic aromatic hydrocarbons (PAHs) (Z1-Z3) were synthesized from 2,12-dibromo-7,14-diphenyl-benzo[m]tetraphene (9) as a versatile building block. Their structures were unambiguously confirmed by laser desorption/ionization time-of-flight mass spectrometry, 1 H NMR, Raman, and Fourier-transformed infrared (FTIR) spectroscopies as well as scanning tunneling microscopy. The fingerprint vibrational modes were elucidated with theoretical support. The edge- and size-dependent optical properties were characterized by UV-Vis absorption and fluorescence spectroscopy and DFT calculations. Moreover, ultrafast transient absorption spectroscopy revealed distinct modulation of the photophysical properties upon π-extension from Z1 to Z2, the latter having a gulf edge.

Synthesis of zigzag- and fjord-edged nanographene with dual amplified spontaneous emission.

We report the synthesis of a dibenzodinaphthocoronene (DBDNC) derivative as a novel nanographene with armchair, zigzag, and fjord edges, which was characterized by NMR and X-ray crystallography as well as infrared (IR) and Raman spectroscopies. Ultrafast transient absorption (TA) spectroscopy revealed the presence of stimulated emission signals at 655 nm and 710 nm with a relatively long lifetime, which resulted in dual amplified spontaneous emission (ASE) bands under ns-pulsed excitation, indicating the promise of DBNDC as a near-infrared (NIR) fluorophore for photonics. Our results provide new insight into the design of nanographene with intriguing optical properties by incorporating fjord edges.

Near-Infrared Plasmon-Induced Hot Electron Extraction Evidence in an Indium Tin Oxide Nanoparticle/Monolayer Molybdenum Disulfide Heterostructure.

In this work, we observe plasmon-induced hot electron extraction in a heterojunction between indium tin oxide nanocrystals and monolayer molybdenum disulfide. We study the sample with ultrafast differential transmission, exciting the sample at 1750 nm where the intense localized plasmon surface resonance of the indium tin oxide nanocrystals is and where the monolayer molybdenum disulfide does not absorb light. With the excitation at 1750 nm, we observe the excitonic features of molybdenum disulfide in the visible range, close to the exciton of molybdenum disulfide. Such a phenomenon can be ascribed to a charge transfer between indium tin oxide nanocrystals and monolayer molybdenum disulfide upon plasmon excitation. These results are a first step toward the implementation of near-infrared plasmonic materials for photoconversion.

Deciphering Photoinduced Charge Transfer Dynamics in a Cross-Linked Graphene-Dye Nanohybrid.

The search for synthetic materials that mimic natural photosynthesis by converting solar energy into other more useful forms of energy is an ever-growing research endeavor. Graphene-based materials, with their exceptional electronic and optical properties, are exemplary candidates for high-efficiency solar energy harvesting devices. High photoactivity can be conveniently achieved by functionalizing graphene with small molecule organic semiconductors whose band-gaps can be tuned by structural modification, leading to interactions between the π-conjugated electronic systems in both the semiconductor and graphene. Here we investigate the ultrafast transient optical properties of a cross-linked graphene-dye (diphenyl-dithiophenediketopyrrolopyrrole) nanohybrid material, in which oligomers of the organic semiconductor dye are covalently bound to a random network of few-layer graphene flakes, and compare the results to those obtained for the reference dye monomer. Using a combination of ultrafast transient absorption and two-dimensional electronic spectroscopy, we provide substantial evidence for photoinduced charge transfer that occurs within 18 ps in the nanohybrid system. Notably, subpicosecond photoinduced torsional relaxation observed in the constituent dye monomer is absent in the cross-linked nanohybrid system. Through density functional theory calculations, we compare the competing effects of covalent bonding, increasing conjugation length, and the presence of multiple graphene flakes. We find evidence that the observed ultrafast charge transfer process occurs through a superexchange mechanism in which the oligomeric dye bridge provides virtual states enabling charge transfer between graphene-dye covalent bond sites.

Effective medium optical modelling of indium tin oxide nanocrystal films.

Doped semiconductor nanocrystal-based thin films are widely used for many applications, such as screens, electrochromic windows, light emitting diodes, and solar cells. Herein, we have employed spectroscopic ellipsometry to measure and model the complex dielectric response of indium tin oxide films fabricated by nanocrystal deposition and sintering. The films could be modelled as Bruggemann effective media, allowing estimation of the nanoscale interstitial porosity of the structure. The effective dielectric constants show the possibility of tuning the plasma frequency and the epsilon-near zero condition of the film.

Excited states engineering enables efficient near-infrared lasing in nanographenes.

The spectral overlap between stimulated emission (SE) and absorption from dark states (i.e. charges and triplets) especially in the near-infrared (NIR), represents one of the most effective gain loss channels in organic semiconductors. Recently, bottom-up synthesis of atomically precise graphene nanostructures, or nanographenes (NGs), has opened a new route for the development of environmentally and chemically stable materials with optical gain properties. However, also in this case, the interplay between gain and absorption losses has hindered the attainment of efficient lasing action in the NIR. Here, we demonstrate that the introduction of two fluoranthene imide groups to the NG core leads to a more red-shifted emission than the precursor NG molecule (685 vs. 615 nm) and also with a larger Stokes shift (45 nm vs. 2 nm, 1026 cm-1vs. 53 cm-1, respectively). Photophysical results indicate that, besides the minimisation of ground state absorption losses, such substitution permits to suppress the detrimental excited state absorption in the NIR, which likely arises from a dark state with charge-transfer character and triplets. This has enabled NIR lasing (720 nm) from all-solution processed distributed feedback devices with one order of magnitude lower thresholds than those of previously reported NIR-emitting NGs. This study represents an advance in the field of NGs and, in general, organic semiconductor photonics, towards the development of cheap and stable NIR lasers.

Engineering of the spin on dopant process on silicon on insulator substrate.

We report on a systematic analysis of phosphorus diffusion in silicon on insulator thin film via spin-on-dopant process (SOD). This method is used to provide an impurity source for semiconductor junction fabrication. The dopant is first spread into the substrate via SOD and then diffused by a rapid thermal annealing process. The dopant concentration and electron mobility were characterized at room and low temperature by four-probe and Hall bar electrical measurements. Time-of-flight-secondary ion mass spectroscopy was performed to estimate the diffusion profile of phosphorus for different annealing treatments. We find that a high phosphorous concentration (greater than 1020 atoms cm-3) with a limited diffusion of other chemical species and allowing to tune the electrical properties via annealing at high temperature for short time. The ease of implementation of the process, the low cost of the technique, the possibility to dope selectively and the uniform doping manufactured with statistical process control show that the methodology applied is very promising as an alternative to the conventional doping methods for the implementation of optoelectronic devices.

Bringing the interaction of silver nanoparticles with bacteria to light.

In past decades, the exploitation of silver nanoparticles in novel antibacterial and detection devices has risen to prominence, owing to the well-known specific interaction of silver with bacteria. The vast majority of the investigations focus on the investigation over the mechanism of action underpinning bacterial eradication, while few efforts have been devoted to the study of the modification of silver optical properties upon interaction with bacteria. Specifically, given the characteristic localized surface plasmon resonance of silver nanostructures, which is sensitive to changes in the charge carrier density or in the dielectric environment, these systems can offer a handle in the detection of bacteria pathogens. In this review, we present the state of art of the research activity on the interaction of silver nanoparticles with bacteria, with strong emphasis on the modification of their optical properties. This may indeed lead to easy color reading of bacterial tests and pave the way to the development of nanotechnologic silver-based bacterial detection systems and drug-screening platforms.

Anisotropic Complex Refractive Indices of Atomically Thin Materials: Determination of the Optical Constants of Few-Layer Black Phosphorus.

In this work, studies of the optical constants of monolayer transition metal dichalcogenides and few-layer black phosphorus are briefly reviewed, with particular emphasis on the complex dielectric function and refractive index. Specifically, an estimate of the complex index of refraction of phosphorene and few-layer black phosphorus is given. The complex index of refraction of this material was extracted from differential reflectance data reported in the literature by employing a constrained Kramers-Kronig analysis combined with the transfer matrix method. The reflectance contrast of 1-3 layers of black phosphorus on a silicon dioxide/silicon substrate was then calculated using the extracted complex indices of refraction.

The ultrafast onset of exciton formation in 2D semiconductors.

The equilibrium and non-equilibrium optical properties of single-layer transition metal dichalcogenides (TMDs) are determined by strongly bound excitons. Exciton relaxation dynamics in TMDs have been extensively studied by time-domain optical spectroscopies. However, the formation dynamics of excitons following non-resonant photoexcitation of free electron-hole pairs have been challenging to directly probe because of their inherently fast timescales. Here, we use extremely short optical pulses to non-resonantly excite an electron-hole plasma and show the formation of two-dimensional excitons in single-layer MoS2 on the timescale of 30 fs via the induced changes to photo-absorption. These formation dynamics are significantly faster than in conventional 2D quantum wells and are attributed to the intense Coulombic interactions present in 2D TMDs. A theoretical model of a coherent polarization that dephases and relaxes to an incoherent exciton population reproduces the experimental dynamics on the sub-100-fs timescale and sheds light into the underlying mechanism of how the lowest-energy excitons, which are the most important for optoelectronic applications, form from higher-energy excitations. Importantly, a phonon-mediated exciton cascade from higher energy states to the ground excitonic state is found to be the rate-limiting process. These results set an ultimate timescale of the exciton formation in TMDs and elucidate the exceptionally fast physical mechanism behind this process.

Dual Amplified Spontaneous Emission and Lasing from Nanographene Films.

Chemically synthesized zigzag-edged nanographenes (NG) have recently demonstrated great success as the active laser units in solution-processed organic distributed feedback (DFB) lasers. Here, we report the first observation of dual amplified spontaneous emission (ASE) from a large-size NG derivative (with 12 benzenoid rings) dispersed in a polystyrene film. ASE is observed simultaneously at the 685 and 739 nm wavelengths, which correspond to different transitions of the photoluminescence spectrum. Ultrafast pump-probe spectroscopy has been used to ascertain the underlying photophysical processes taking place in the films. DFB lasers, based on these materials and top-layer nanostructured polymeric resonators (i.e., one or two-dimensional surface relief gratings), have been fabricated and characterized. Lasers emitting close to either one of the two possible ASE wavelengths, or simultaneously at both of them, have been prepared by proper selection of the resonator parameters.

Integration of bio-responsive silver in 1D photonic crystals: towards the colorimetric detection of bacteria.

The colour purity and versatility of fabrication of one-dimensional photonic crystals (1D PhCs) make them ideal candidates for colorimetric sensing of a variety of analytes. For instance, the detection of bacterial contaminants in food via colorimetric sensors can be highly appealing, as most of the existing detection techniques are in general time-consuming and the read-out requires specialised personnel. Here, we present a colorimetric sensor based on hybrid plasmonic/photonic 1D crystals. We demonstrate that the modification of the silver plasmon resonance brought about by the effective silver/bacterium interaction can be translated into the visible spectral region, producing a change in the structural colour. In addition, we observe a superior colorimetric sensitivity against the Gram negative Escherichia coli compared to the Gram positive Micrococcus luteus, a result that we attribute to the more efficient electrostatic interaction and cellular adhesion between the silver surface and the Gram-negative bacteria outer membrane. This approach demonstrates that in principle an easy colorimetric detection of bacterial contaminants can be achieved through the use of bio-responsive plasmonic materials, such as silver, whose selective electrostatic interaction with bacterial cell wall is well-known and occurs without the need of chemical functionalisation.

Large scale indium tin oxide (ITO) one dimensional gratings for ultrafast signal modulation in the visible spectral region.

Indium tin oxide (ITO) is a heavily doped semiconductor with a plasmonic response in the near infrared region. When exposed to light, the distribution of conduction band electron induces a change in the real and imaginary parts of the dielectric permittivity. The coupling of the electromagnetic waves with the electrons in the conduction band of metallic nanostructures with ultrashort light pulses results in a nonlinear plasmonic response. Such optical modulation occurring on ultrafast time scales, e.g. picosecond response times, can be exploited and used to create integrated optical components with terahertz modulation speed. Here, we present a photophysical study on a one dimensional ITO grating, realized using a femtosecond micromachining process, a very industrially accessible technology. The geometries, dimensions and pitch of the various gratings analyzed are obtained by means of direct ablation in a controlled atmosphere of a homogeneous thin layer of ITO deposited on a glass substrate. The pitch has been selected in order to obtain a higher order of the photonic band gap in the visible spectral region. Femtosecond micromachining technology guarantees precision, repeatability and extreme manufacturing flexibility. By means of ultrafast pump-probe spectroscopy, we characterize both the plasmon and inter-band temporal dynamics. We observe a large optical nonlinearity of the ITO grating in the visible range, where the photonic band gap occurs, when pumped at the surface plasmon resonance in the near infrared (1500 nm) region. All together, we show the possibility of all-optical signal modulation with heavily doped semiconductors in their transparency window with a picosecond response time through the formation of ITO grating structures.

Colloidal Bi-Doped Cs2Ag1-x Na x InCl6 Nanocrystals: Undercoordinated Surface Cl Ions Limit their Light Emission Efficiency.

Understanding and tuning the ligand shell composition in colloidal halide perovskite nanocrystals (NCs) has been done systematically only for Pb-based perovskites, while much less is known on the surface of Pb-free perovskite systems. Here, we reveal the ligand shell architecture of Bi-doped Cs2Ag1-x Na x InCl6NCs via nuclear magnetic resonance analysis. This material, in its bulk form, was found to have a photoluminescence quantum yield (PLQY) as high as 86%, a record value for halide double perovskites. Our results show that both amines and carboxylic acids are present and homogeneously distributed over the surface of the NCs. Notably, even for an optimized surface ligand coating, achieved by combining dodecanoic acid and decylamine, a maximum PLQY value of only 37% is reached, with no further improvements observed when exploiting post-synthesis ligand exchange procedures (involving Cs-oleate, different ammonium halides, thiocyanates and sulfonic acids). Our density functional theory calculations indicate that, even with the best ligands combination, a small fraction of unpassivated surface sites, namely undercoordinated Cl ions, is sufficient to create deep trap states, opposite to the case of Pb-based perovskites that exhibit much higher defect tolerance. This was corroborated by our transient absorption measurements, which showed that an ultrafast trapping of holes (most likely mediated by surface Cl-trap states) competes with their localization at the AgCl6 octahedra, from where, instead, they can undergo an optically active recombination yielding the observed PL emission. Our results highlight that alternative surface passivation strategies should be devised to further optimize the PLQY of double perovskite NCs, which might include their incorporation inside inorganic shells.

Hexa-peri-benzocoronene with two extra K-regions in an ortho-configuration.

There are three possible isomers for hexa-peri-hexabenzocoronene (HBC) with two extra K-regions, but only two of them have been reported, namely with the meta- and para-configurations. Herein, we describe the synthesis of HBC 4 with two extra K-regions in the ortho-configuration, forming a longer zigzag edge compared with the other two isomers. The structure of 4 was validated by laser desorption/ionization time-of-flight mass analysis and nuclear magnetic resonance spectra, as well as Raman and infrared spectroscopies supported by density functional theory calculations. The optical properties of 4 were investigated by UV/vis absorption and ultrafast transient absorption spectroscopy. Together with the analysis of aromaticity, the influence of the zigzag edge on the π-conjugation pathway and HOMO-LUMO gaps of the three isomers were investigated.