Assembly of Covalent Organic Frameworks into Colloidal Photonic Crystals.

Self-assembly of colloidal particles into ordered superstructures is an important strategy to discover new materials, such as catalysts, plasmonic sensing materials, storage systems, and photonic crystals (PhCs). Here we show that porous covalent organic frameworks (COFs) can be used as colloidal building particles to fabricate porous PhCs with an underlying face-centered cubic (fcc) arrangement. We demonstrate that the Bragg reflection of these can be tuned by controlling the size of the COF particles and that species can be adsorbed within the pores of the COF particles, which in turn alters the Bragg reflection. Given the vast number of existing COFs, with their rich properties and broad modularity, we expect that our discovery will enable the development of colloidal PhCs with unprecedented functionality.

Fano-Like Resonance from Disorder Correlation in Vacancy-Doped Photonic Crystals.

By preparing colloidal crystals with random missing scatterers, crystals are created where disorder is embodied as vacancies in an otherwise perfect lattice. In this special system, there is a critical defect concentration where light propagation undergoes a transition from an all but perfect reflector (for the spectral range defined by the Bragg condition), to a metamaterial exhibiting an enhanced transmission phenomenon. It is shown that this behavior can be phenomenologically described in terms of Fano-like resonances. The results show that the Fano's parameter q experiences a sign change signaling the transition from a perfect crystal exhibiting a reflectance Bragg peak, through a state where background scattering is maximum and Bragg reflectance reaches a minimum to a point where the system reenters a low scattering state recovering ordinary Bragg diffraction. A simple dipolar model considering the correlation between scatterers and vacancies is proposed and the reported evolution of the Fano-like scattering is explained in terms of the emerging covariance between the optical paths and polarizabilities and the effect of field enhancement in photonic crystal (PhC) defects.

Tuning the emission properties of electrically pumped semiconductor random lasers via controlled pulsed laser ablation.

Electrically pumped random lasers with distributed feedback can be obtained by introducing random defects into the device active layer, modifying the epitaxial growth process and losing the ease of fabrication potentially offered by disordered structures. We recently demonstrated an alternative and more practical approach in which random lasing emission is obtained from a modified Fabry-Perot laser diode after pulsed laser ablation of its output mirror. Here, we improve our fabrication technique by sweeping the ablating laser beam along the output mirror at different speeds and with different pulse energies, obtaining control over the total energy delivered at each point. We optimize the ablation parameters by evaluating the device performances in terms of lasing threshold and output power and we present the device emission characteristics. The proposed technique is tunable, fast and reliable, allowing the fabrication of devices with different properties by proper selection of the ablation parameters.

Vacancies in Self-Assembled Crystals: An Archetype for Clusters Statistics at the Nanoscale.

Complex systems involving networks have attracted strong multidisciplinary attention since they are predicted to sustain fascinating phase transitions in the proximity of the percolation threshold. Developing stable and compact archetypes that allow one to experimentally study physical properties around the percolation threshold remains a major challenge. In nanoscale systems, this achievement is rare since it is tied to the ability to control the intentional disorder and perform a vast statistical analysis of cluster configurations. Here, a self-assembly method to fabricate perfectly ordered structures where random defects can be introduced is presented. Building binary crystals from two types of dielectric nanospheres and selectively removing one of them creates vacancies at random lattice positions that form a complex network of clusters. Vacancy content can be easily controlled and raised even beyond the percolation threshold. In these structures, the distribution of cluster sizes as a function of vacancy density is analyzed. For moderate concentrations, it is found to be homogeneous throughout the structure and in good agreement with the assumption of a random vacancy distribution.

Template-Free, Surfactant-Mediated Orientation of Self-Assembled Supercrystals of Metal-Organic Framework Particles.

Mesoscale self-assembly of particles into supercrystals is important for the design of functional materials such as photonic and plasmonic crystals. However, while much progress has been made in self-assembling supercrystals adopting diverse lattices and using different types of particles, controlling their growth orientation on surfaces has received limited success. Most of the latter orientation control has been achieved via templating methods in which lithographic processes are used to form a patterned surface that acts as a template for particle assembly. Herein, a template-free method to self-assemble (111)-, (100)-, and (110)-oriented face-centered cubic supercrystals of the metal-organic framework ZIF-8 particles by adjusting the amount of surfactant (cetyltrimethylammonium bromide) used is described. It is shown that these supercrystals behave as photonic crystals whose properties depend on their growth orientation. This control on the orientation of the supercrystals dictates the orientation of the composing porous particles that might ultimately facilitate pore orientation on surfaces for designing membranes and sensors.

A Self-Assembled 2D Thermofunctional Material for Radiative Cooling.

The regulation of temperature is a major energy-consuming process of humankind. Today, around 15% of the global-energy consumption is dedicated to refrigeration and this figure is predicted to triple by 2050, thus linking global warming and cooling needs in a worrying negative feedback-loop. Here, an inexpensive solution is proposed to this challenge based on a single layer of silica microspheres self-assembled on a soda-lime glass. This 2D crystal acts as a visibly translucent thermal-blackbody for above-ambient radiative cooling and can be used to improve the thermal performance of devices that undergo critical heating during operation. The temperature of a silicon wafer is found to be 14 K lower during daytime when covered with the thermal emitter, reaching an average temperature difference of 19 K when the structure is backed with a silver layer. In comparison, the soda-lime glass reference used in the measurements lowers the temperature of the silicon by just 5 K. The cooling power of this simple radiative cooler under direct sunlight is found to be 350 W m-2 when applied to hot surfaces with relative temperatures of 50 K above the ambient. This is crucial to radiatively cool down devices, i.e., solar cells, where an increase in temperature has drastic effects on performance.

Random lasing emission tailored by femtosecond and picosecond pulsed polymer ablation.

We report the realization of random lasers with spatially localized feedback in which the average number of lasing modes is tuned via the fabrication process. The scattering elements required for optical feedback are obtained by short-pulsed laser ablation. By varying the pulse parameters, we control the scattering properties of the induced defects and, thus, the emission spectra. We demonstrate a large variety of spectral signatures typical of resonant random lasing with sub-nanometer linewidths, low thresholds (about 40 pJ/µm2), and single-to-multimode emission. Our simple approach allows us to obtain optical resonators with sharp linewidths at frequencies covering the entire gain window for multiple applications.

Seeded Synthesis of Monodisperse Core-Shell and Hollow Carbon Spheres.

Monodisperse carbon spheres between 500 and 900 nm are hydrothermally synthesized from glucose on polystyrene seeds. Control over temperature, time, glucose concentration, and seed size yields hybrid spheres without aggregation and no additional spheres population. Pyrolysis transforms the hybrid into hollow carbon spheres preserving monodispersity. This approach provides a basis for functional carbon spheres applicable in photonics and energy storage.

Emission regimes of random lasers with spatially localized feedback.

We report the experimental results obtained with a novel architecture for random lasing, in which the active material, free of scatterers, is placed between two large scattering regions. Lasing emission is investigated as a function of the illuminated area of the scattering regions, obtaining typical "resonant" and "non-resonant" random lasing spectra, depending on the device geometry. We propose a theoretical approach for the understanding of the observed phenomena, modelling the scattering elements with arbitrary spectral profiles in amplitude and phase and considering strong coupling between lasing modes. Good agreement between experiments and simulation results is obtained.

Large area resonant feedback random lasers based on dye-doped biopolymer films.

We report resonant feedback random lasing from dye-doped biopolymer films, consisting of a deoxyribonucleic acid-cetyltrimethylammonium (DNA-CTMA) complex doped with DCM dye. In the proposed devices, the optical feedback for random lasing is given by scattering centers randomly positioned along the edges of the active area. Scattering elements are either titanium dioxide nanoparticles or random defects at the interface between active polymer and air. Different emission spectra are observed, depending on the geometry of the excited area. A single random resonator with dimensions of 2.6 mm x 0.65 mm is fabricated and random emission with resonant feedback is obtained by uniformly pumping the full device.

Water-dependent micromechanical and rheological properties of silica colloidal crystals studied by nanoindentation.

Here we show the suitability of nanoindentation to study in detail the micromechanical response of silica colloidal crystals (CCs). The sensitivity to displacements smaller than the submicrometer spheres size, even resolving discrete events and superficial features, revealed particulate features with analogies to atomic crystals. Significant robustness, long-range structural deformation, and large energy dissipation were found. Easily implemented temperature/rate-dependent nanoindentation quantified the paramount role of adsorbed water endowing silica CCs with properties of wet granular materials like viscoplasticity. A novel "nongranular" CC was fabricated by substituting capillary bridges with silica necks to directly test water-independent mechanical response. Silica CCs, as specific (nanometric, ordered) wet granular assemblies with well-defined configuration, may be useful model systems for granular science and capillary cohesion at the nanoscale.

Artificial Intelligence and Advanced Materials.

Artificial intelligence (AI) is gaining strength, and materials science can both contribute to and profit from it. In a simultaneous progress race, new materials, systems, and processes can be devised and optimized thanks to machine learning (ML) techniques, and such progress can be turned into innovative computing platforms. Future materials scientists will profit from understanding how ML can boost the conception of advanced materials. This review covers aspects of computation from the fundamentals to directions taken and repercussions produced by computation to account for the origins, procedures, and applications of AI. ML and its methods are reviewed to provide basic knowledge of its implementation and its potential. The materials and systems used to implement AI with electric charges are finding serious competition from other information-carrying and processing agents. The impact these techniques have on the inception of new advanced materials is so deep that a new paradigm is developing where implicit knowledge is being mined to conceive materials and systems for functions instead of finding applications to found materials. How far this trend can be carried is hard to fathom, as exemplified by the power to discover unheard of materials or physical laws buried in data.

Simultaneous generation of second to fifth harmonic conical beams in a two dimensional nonlinear photonic crystal.

Broadly tunable multiple high-harmonic conical beams have been generated by means of a multistep χ(2) cascade processes in a two dimensional nonlinear photonic crystal. The nonlinear structure consists of a square lattice of inverted hexagonal domains with diameters and distances between domains as low as 1 µm. The large number of reciprocal lattice vectors provided by both the square nonlinear structure and the hexagonal shaped domains, along with imperfections on the size and shape of the individual domains make possible the simultaneous generation of second up to fifth harmonic conical beams in a single nonlinear structure by using different types of phase matching geometries. The frequency response can be tuned in an extremely large spectral range, and continuous generation of nonlinear conical beams covering the whole visible spectral region can be achieved. Further, the same photon energy can be generated at different orders, so that concentrically emitted conical beams with angular dispersion as large as Δθ = 50° can be observed. The results highlight the significance of highly controlled engineered 2D nonlinear structures to generate advanced multi-photon devices with large spatial and spectral tunable response.

Qualitative and quantitative analysis of crystallographic defects present in 2D colloidal sphere arrays.

In this work, we present a study of the typical spontaneous defects present in self-assembled colloidal monolayers grown from polystyrene and silica microspheres. The quality of two-dimensional crystals from different colloidal suspensions of beads around 1 µm in diameter has been studied qualitatively and quantitatively, evaluated in 2D hexagonal arrays at different scales through Fourier analysis of SEM images and optical characterization. The crystallographic defects are identified to better understand their origin and their effects on the crystal quality, as well as to find the best conditions colloidal suspensions must fulfill to achieve optimal quality samples.

One-step-process composite colloidal monolayers and further processing aiming at porous membranes.

Composite materials consisting of a monolayer of polystyrene spheres (diameters of 430 and 520 nm) and porous silica, filling in the interstices, have been fabricated and characterized. The proposed growth method introduces some novelties as far as the fabrication of this kind of monolayers is concerned, as it probes the compatibility of coassembly (in which a silica precursor, tetraethyl orthosilicate (TEOS), is added to the base colloid) with confined growth in a wedge-shaped cell, while profiting from the advantages of both techniques. Using this method, it is possible to fabricate the composite monolayer in a single growth step. A systematic study of the influence of TEOS concentration in the initial colloid was performed in order to improve the quality of the two-dimensional crystals produced. Thus, it was demonstrated that the two methods are compatible. Furthermore, the composites were then subjected to thermal treatment so that the polymer is removed to reveal the inverse structure. After the calcination the membranes still present very good quality and so the proposed approach is effective for the fabrication of porous membranes. A comparison of reflectance spectra, between composite monolayers fabricated using this method and composites achieved by infiltrating polystyrene bare opals with silica chemical vapor deposition, is also established. The procedure presented is expected to establish the route for an easier and quicker fabrication of inverse monolayers of high refractive index materials with applications in light control.

Water-dependent photonic bandgap in silica artificial opals.

Some characteristics of silica--based structures-like the photonic properties of artificial opals formed by silica spheres--can be greatly affected by the presence of adsorbed water. The reversible modification of the water content of an opal is investigated here by moderate heating (below 300 °C) and measuring in situ the changes in the photonic bandgap. Due to reversible removal of interstitial water, large blueshifts of 30 nm and a bandgap narrowing of 7% are observed. The latter is particularly surprising, because water desorption increases the refractive index contrast, which should lead instead to bandgap broadening. A quantitative explanation of this experiment is provided using a simple model for water distribution in the opal that assumes a nonclose-packed fcc structure. This model further predicts that, at room temperature, about 50% of the interstitial water forms necks between nearest-neighbor spheres, which are separated by 5% of their diameter. Upon heating, dehydration predominantly occurs at the sphere surfaces (in the opal voids), so that above 65 °C the remaining water resides exclusively in the necks. A near-close-packed fcc arrangement is only achieved above 200 °C. The high sensitivity to water changes exhibited by silica opals, even under gentle heating of few degrees, must be taken into account for practical applications. Remarkably, accurate control of the distance between spheres--from 16 to 1 nm--is obtained with temperature. In this study, novel use of the optical properties of the opal is made to infer quantitative information about water distribution within silica beads and dehydration phenomena from simple reflection spectra. Taking advantage of the well-defined opal morphology, this approach offers a simple tool for the straightforward investigation of generic adsorption-desorption phenomena, which might be extrapolated to many other fields involving capillary condensation.

Measurement of transport mean-free path of light in thin systems.

We extensively investigate in-plane light diffusion in systems with thicknesses larger than but comparable with the transport mean free path. By exploiting amplified spontaneous emission from dye molecules placed in the same holder of the sample, we obtain a directional probe beam precisely aligned to the sample plane. By comparing spatial intensity distribution of laterally leaking photons with predictions from random walk simulations, we extract accurate values of transport mean free path, opening the way to the investigation of a previously inaccessible kind of sample.

Three regimes of water adsorption in annealed silica opals and optical assessment.

Physisorbed and structurally bound (surface and internal) water in silica opals are distinguished and quantified by thermogravimetry. By controlled dehydroxylation with thermal annealing, we correlate these forms of water with the silica chemistry. In particular, we find that the silica capability to physically adsorb water from ambient moisture exhibits three regimes, associated with the distinct condensation behavior of bonded and unbonded surface silanols. Features in both opal IR absorbance and photonic band gap reproduce the physisorbed water regimes. This allows direct assessment of the water content and its evolution just by routine optical spectroscopy, being a useful tool for local and nondestructive analysis of colloidal silica. Besides, this provides a simple recipe for accurate tuning of the opal photonic band gap (about 10% in position and width) by just selecting the annealing temperature.

Imbibition and dewetting of silica colloidal crystals: An NMR relaxometry study.

HYPOTHESIS: The wettability of the inner surfaces in a porous network is challenging to be accessed but essential to understand the complex performance of e.g. particulate systems. EXPERIMENTS: Here we investigate the water behavior in the macroporous (50-100 nm) voids of dense particle packings by performing low-field 1H NMR relaxometry in solid silica colloid crystals. The systems chosen guarantee a regular, known void size distribution with controllable water affinity (through thermal annealing), where the NMR experiment clearly discriminates the void water from micropore or bound water contributions, allowing separate monitoring. FINDINGS: Analysis of the saturated state indicates that the interparticle voids are completely filled after imbibition, even for less hydrophilic spheres. Due to the interaction with the silica surface, proton relaxation in void water is up to 100 times faster than that in bulk water, serving for assessment of the hydrophilicity within the sample. The relaxation time evolution upon dewetting provides an empirical measurement of the wettability inside the ensemble, revealing a progressively inhomogeneous wetting of increasingly hydrophobic surfaces. Our results provide insight into the imbibition state and dewetting performance in meso- and macroporous systems, with emphasis in the marked influence of the surface nature on the pore wetting distribution.

Optical gain in DNA-DCM for lasing in photonic materials.

We present a detailed study of the gain length in an active medium obtained by doping of DNA strands with 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran dye molecules. The superior thermal stability of the composite and its low quenching permit one to obtain an optical gain coefficient larger than 300 cm(-1). We also demonstrate that such an active material is feasible for the infiltration into photonic nanostructures, allowing one to obtain fluorescent photonic crystals and promising lasing properties.