Condensation or Desublimation: Nanolevel Structural Look on Two Frost Formation Pathways on Surfaces with Different Wettabilities.

Processes of water condensation and desublimation on solid surfaces are ubiquitous in nature and essential for various industrial applications, which are crucial for their performance. Despite their significance, these processes are not well understood due to the lack of methods that can provide insight at the nanolevel into the very first stages of phase transitions. Taking advantage of synchrotron grazing-incidence wide-angle X-ray scattering (GIWAXS) and environmental scanning electron microscopy (ESEM), two pathways of the frosting process from supersaturated vapors were studied in real time for substrates with different wettabilities ranging from highly hydrophilic to superhydrophobic. Within GIWAXS, a fully quantitative structural and orientational characterization of the undergoing phase transition reveals the information on degree of crystallinity of the new phase and determines the ordering at the surfaces and inside the films at the initial stages of water/ice nucleation from vapor onto the substrates. The diversity of frosting scenarios, including direct desublimation from the vapor and two-stage condensation-freezing processes, was observed by both GIWAXS and ESEM for different combinations of substrate wettability and vapor supersaturations. The classical nucleation theory straightforwardly predicts the pathway of the phase transition for hydrophobic and superhydrophobic substrates. The case of hydrophilic substrates is more intricate because the barriers in Gibbs free energy for nucleating both liquid and solid embryos are close to each other and comparable to thermal energy kBT. At that end, classical nucleation theory allows concluding a relation between contact angles for ice and water embryos on the basis of the observed frosting pathway.

Controllable Anchoring of Graphitic Carbon Nitride on MnO2 Nanoarchitectures for Oxygen Evolution Electrocatalysis.

The design and fabrication of eco-friendly and cost-effective (photo)electrocatalysts for the oxygen evolution reaction (OER) is a key research goal for a proper management of water splitting to address the global energy crisis. In this work, we focus on the preparation of supported MnO2/graphitic carbon nitride (g-CN) OER (photo)electrocatalysts by means of a novel preparation strategy. The proposed route consists of the plasma enhanced-chemical vapor deposition (PE-CVD) of MnO2 nanoarchitectures on porous Ni scaffolds, the anchoring of controllable g-CN amounts by an amenable electrophoretic deposition (EPD) process, and the ultimate thermal treatment in air. The inherent method versatility and flexibility afforded defective MnO2/g-CN nanoarchitectures, featuring a g-CN content and nano-organization tunable as a function of EPD duration and the used carbon nitride precursor. Such a modulation had a direct influence on OER functional performances, which, for the best composite system, corresponded to an overpotential of 430 mV at 10 mA/cm2, a Tafel slope of ≈70 mV/dec, and a turnover frequency of 6.52 × 10-3 s-1, accompanied by a very good time stability. The present outcomes, comparing favorably with previous results on analogous systems, were rationalized on the basis of the formation of type-II MnO2/g-CN heterojunctions, and yield valuable insights into this class of green (photo)electrocatalysts for end uses in solar-to-fuel conversion and water treatment.

Towards All-Non-Vacuum-Processed Photovoltaic Systems: A Water-Based Screen-Printed Cu(In,Ga)Se2 Photoabsorber with a 6.6% Efficiency.

During the last few decades, major advances have been made in photovoltaic systems based on Cu(In,Ga)Se2 chalcopyrite. However, the most efficient photovoltaic cells are processed under high-energy-demanding vacuum conditions. To lower the costs and facilitate high-throughput production, printing/coating processes are proving to be effective solutions. This work combined printing, coating, and chemical bath deposition processes of photoabsorber, buffer, and transparent conductive layers for the development of solution-processed photovoltaic systems. Using a sustainable approach, all inks were formulated using water and ethanol as solvents. Screen printing of the photoabsorber on fluorine-doped tin-oxide-coated glass followed by selenization, chemical bath deposition of the cadmium sulfide buffer, and final sputtering of the intrinsic zinc oxide and aluminum-doped zinc oxide top conductive layers delivered a 6.6% maximum efficiency solar cell, a record for screen-printed Cu(In,Ga)Se2 solar cells. On the other hand, the all-non-vacuum-processed device with spray-coated intrinsic zinc-oxide- and tin-doped indium oxide top conductive layers delivered a 2.2% efficiency. The given approaches represent relevant steps towards the fabrication of sustainable and efficient Cu(In,Ga)Se2 solar cells.

Noble-Metal Nanoparticle-Embedded Silicon Nanogratings via Single-Step Laser-Induced Periodic Surface Structuring.

Here, we show that direct femtosecond laser nanostructuring of monocrystalline Si wafers in aqueous solutions containing noble-metal precursors (such as palladium dichloride, potassium hexachloroplatinate, and silver nitrate) allows for the creation of nanogratings decorated with mono- (Pd, Pt, and Ag) and bimetallic (Pd-Pt) nanoparticles (NPs). Multi-pulse femtosecond-laser exposure was found to drive periodically modulated ablation of the Si surface, while simultaneous thermal-induced reduction of the metal-containing acids and salts causes local surface morphology decoration with functional noble metal NPs. The orientation of the formed Si nanogratings with their nano-trenches decorated with noble-metal NPs can be controlled by the polarization direction of the incident laser beam, which was justified, for both linearly polarized Gaussian and radially (azimuthally) polarized vector beams. The produced hybrid NP-decorated Si nanogratings with a radially varying nano-trench orientation demonstrated anisotropic antireflection performance, as well as photocatalytic activity, probed by SERS tracing of the paraaminothiophenol-to-dimercaptoazobenzene transformation. The developed single-step maskless procedure of liquid-phase Si surface nanostructuring that proceeds simultaneously with the localized reduction of noble-metal precursors allows for the formation of hybrid Si nanogratings with controllable amounts of mono- and bimetallic NPs, paving the way toward applications in heterogeneous catalysis, optical detection, light harvesting, and sensing.

Dual-Band Coupling of Phonon and Surface Plasmon Polaritons with Vibrational and Electronic Excitations in Molecules.

Strong coupling (SC) between light and matter excitations bears intriguing potential for manipulating material properties. Typically, SC has been achieved between mid-infrared (mid-IR) light and molecular vibrations or between visible light and excitons. However, simultaneously achieving SC in both frequency bands remains unexplored. Here, we introduce polaritonic nanoresonators (formed by h-BN layers on Al ribbons) hosting surface plasmon polaritons (SPPs) at visible frequencies and phonon polaritons (PhPs) at mid-IR frequencies, which simultaneously couple to excitons and molecular vibrations in an adjacent layer of CoPc molecules, respectively. Employing near-field optical nanoscopy, we demonstrate the colocalization of near fields at both visible and mid-IR frequencies. Far-field transmission spectroscopy of the nanoresonator structure covered with a layer of CoPc molecules shows clear mode splittings in both frequency ranges, revealing simultaneous SPP-exciton and PhP-vibron coupling. Dual-band SC may offer potential for manipulating coupling between exciton and molecular vibration in future optoelectronics, nanophotonics, and quantum information applications.

Multigram-Scale Production of Hybrid Au-Si Nanomaterial by Laser Ablation in Liquid (LAL) for Temperature-Feedback Optical Nanosensing, Light-to-Heat Conversion, and Anticounterfeit Labeling.

Recent progress in hybrid optical nanomaterials composed of dissimilar constituents permitted an improvement in the performance and functionality of novel devices developed for optoelectronics, catalysis, medical diagnostics, and sensing. However, the rational combination of contrasting materials such as noble metals and semiconductors within individual hybrid nanostructures via a ready-to-use and lithography-free fabrication approach is still a challenge. Here, we report on a two-step synthesis of hybrid Au-Si microspheres generated by laser ablation of silicon in isopropanol followed by laser irradiation of the produced Si nanoparticles in the presence of HAuCl4. Thermal reduction of [AuCl4]- species to a metallic gold phase, along with its subsequent mixing with silicon under laser irradiation, creates a nanostructured material with a unique composition and morphology, as revealed by electron microscopy, tomography, and elemental analysis. A combination of basic plasmonic and nanophotonic materials such as gold and silicon within a single microsphere allows for efficient light-to-heat conversion, as well as single-particle SERS sensing with temperature-feedback modality and expanded functionality. Moreover, the characteristic Raman signal and hot-electron-induced nonlinear photoluminescence coexisting within the novel Au-Si hybrids, as well as the commonly criticized randomness of the nanomaterials prepared by laser ablation in liquid, were proved to be useful for the realization of anticounterfeiting labels based on a physically unclonable function approach.

Ag-Decorated Si Microspheres Produced by Laser Ablation in Liquid: All-in-One Temperature-Feedback SERS-Based Platform for Nanosensing.

Combination of dissimilar materials such as noble metals and common semiconductors within unified nanomaterials holds promise for optoelectronics, catalysis and optical sensing. Meanwhile, difficulty of obtaining such hybrid nanomaterials using common lithography-based techniques stimulates an active search for advanced, inexpensive, and straightforward fabrication methods. Here, we report one-pot one-step synthesis of Ag-decorated Si microspheres via nanosecond laser ablation of monocrystalline silicon in isopropanol containing AgNO3. Laser ablation of bulk silicon creates the suspension of the Si microspheres that host further preferential growth of Ag nanoclusters on their surface upon thermal-induced decomposition of AgNO3 species by subsequently incident laser pulses. The amount of the AgNO3 in the working solution controls the density, morphology, and arrangement of the Ag nanoclusters allowing them to achieve strong and uniform decoration of the Si microsphere surface. Such unique morphology makes Ag-decorated Si microspheres promising for molecular identification based on the surface-enhanced Raman scattering (SERS) effect. In particular, the designed single-particles sensing platform was shown to offer temperature-feedback modality as well as SERS signal enhancement up to 106, allowing reliable detection of the adsorbed molecules and tracing their plasmon-driven catalytic transformations. Considering the ability to control the decoration degree of Si microspheres by Ag nanoclusters via amount of the AgNO3, the developed one-pot easy-to-implement PLAL synthesis holds promise for gram-scale production of high-quality hybrid nanomaterial for various nanophotonics and sensing applications.

Security labeling and optical information encryption enabled by laser-printed silicon Mie resonators.

Fighting against the falsification of valuable items remains a crucial social-threatening challenge stimulating a never-ending search for novel anti-counterfeiting strategies. The demanding security labels must simultaneously address multiple requirements (high density of the recorded information, high protection degree, etc.) and be realized via scalable and inexpensive technologies. Here, the direct reproducible femtosecond-laser patterning of thin glass-supported amorphous (α-)Si films is proposed for optical information encryption and the scalable and highly reproducible fabrication of security labels composed of Raman-active hemispherical Si nanoparticles (NPs). Laser printing conditions allow the precise control of the diameter of the formed NPs ensuring translation of their dipolar Mie resonance position within the entire visible spectral range. Two-temperature molecular dynamics simulations clarify the origin of α-Si NP formation by rupture of the molten Si layer driven by a negative GPa-range pressure near the liquid-solid interface. Arrangement of the laser-printed Mie-resonant NP allows the creation of hidden security labels offering several easy-to-realize information encryption strategies (for example, local laser-induced post-crystallization or mixing Mie-resonant and non-resonant NPs), additional protection modalities, facile Raman mapping readout and dense information recording (up to 60 000 dots per inch) close to the optical diffraction limit. The developed fabrication strategy is simple, inexpensive, and scalable and can be realized based on cheap Earth-abundant materials and commercially-available equipment justifying its practical applicability and attractiveness for anti-counterfeit and security applications.

Entropy-Driven Self-Healing of Metal Oxides Assisted by Polymer-Inorganic Hybrid Materials.

Enabling self-healing of materials is crucially important for saving resources and energy in numerous emerging applications. While strategies for the self-healing of polymers are advanced, mechanisms for semiconducting inorganic materials are scarce due to the lack of suitable healing agents. Here a concept for the self-healing of metal oxides is developed. This concept consists of metal oxide nanoparticle growth inside the bulk of halogenated polymers and their subsequent entropy-driven migration to externally induced defect sites, leading to recovery of the defect. Herein, it is demonstrated that the pool of self-healing materials is expanded to include semiconductors, thereby increasing the reliability and sustainability of functional materials through the use of metal oxides. It is revealed that electrical properties of tin-doped indium oxide can be partially restored upon healing. Such properties are of immediate interest for the further development of transparent flexible electrodes.

Double-Lattice Packing of Pentagonal Gold Bipyramids in Supercrystals with Triclinic Symmetry.

Pentagonal packing is a long-standing issue and a rich mathematical topic, brought to the fore by recent progress in nanoparticle design. Gold pentagonal bipyramids combine fivefold symmetry and anisotropy and their section varies along the length. In this work, colloidal supercrystals of pentagonal gold bipyramids are obtained in a compact arrangement that generalizes the optimal packing of regular pentagons in the plane. Multimodal investigations reveal a two-particle unit cell with triclinic symmetry, a lower symmetry than that of the building blocks. Monte Carlo computer simulations show that this lattice achieves the densest possible packing. Going beyond pentagons, further simulations show an odd-even effect of the number of sides on the packing: odd-sided bipyramids are non-centrosymmetric and require the double-lattice arrangement to recover inversion symmetry. The supercrystals display a facet-dependent optical response that is promising for sensing, metamaterials applications, and for fundamental studies of self-assembly processes.

Deep Subwavelength Laser-Induced Periodic Surface Structures on Silicon as a Novel Multifunctional Biosensing Platform.

Strong light localization inside the nanoscale gaps provides remarkable opportunities for creation of various medical and biosensing platforms stimulating an active search for inexpensive and easily scalable fabrication at a sub-100 nm resolution. In this paper, self-organized laser-induced periodic surface structures (LIPSSs) with the shortest ever reported periodicity of 70 ± 10 nm were directly imprinted on the crystalline Si wafer upon its direct femtosecond-laser ablation in isopropanol. Appearance of such a nanoscale morphology was explained by the formation of a periodic topography on the surface of photoexcited Si driven by interference phenomena as well as subsequent down-scaling of the imprinted grating period via Rayleigh-Taylor hydrodynamic instability. The produced deep subwavelength LIPSSs demonstrate strong anisotropic anti-reflection performance, ensuring efficient delivery of the incident far-field radiation to the electromagnetic "hot spots" localized in the Si nanogaps. This allows realization of various optical biosensing platforms operating via strong interactions of quantum emitters with nanoscale light fields. The demonstrated 80-fold enhancement of spontaneous emission from the attached nanolayer of organic dye molecules and in situ optical tracing of catalytic molecular transformations substantiate bare and metal-capped deep subwavelength Si LIPSSs as a promising inexpensive multifunctional biosensing platform.

Amorphous AlN films grown by ALD from trimethylaluminum and monomethylhydrazine.

The great interest in aluminium nitride thin films has been attributed to their excellent dielectric, thermal and mechanical properties. Here we present the results of amorphous AlN films obtained by atomic layer deposition. We used trimethylaluminum and monomethylhydrazine as the precursors at a deposition temperature of 375-475 °C. The structural and mechanical properties and chemical composition of the synthesized films were investigated in detail by X-ray diffraction, X-ray photoelectron spectroscopy, electron and probe microscopy and nanoindentation. The obtained films were compact and continuous, exhibiting amorphous nature with homogeneous in-depth composition, at an oxygen content of as low as 4 at%. The mechanical properties were comparable to those of AlN films produced by other techniques.

Tailored Co3O4-Based Nanosystems: Toward Photocatalysts for Air Purification.

The adverse effects of NOx (NO + NO2) gases on the environment and human health have triggered the development of sustainable photocatalysts for their efficient removal (De-NOx). In this regard, the present work focuses on supported Co3O4-based nanomaterials fabricated via chemical vapor deposition (CVD), assessed for the first time as photocatalysts for sunlight-activated NO oxidation. A proof-of-principle investigation on the possibility of tailoring material performances by heterostructure formation is explored through deposition of SnO2 or Fe2O3 onto Co3O4 by radio frequency (RF) sputtering. A comprehensive characterization by complementary analytical tools evidences the formation of high-purity columnar Co3O4 arrays with faceted pyramidal tips, conformally covered by very thin SnO2 and Fe2O3 overlayers. Photocatalytic functional tests highlight an appreciable activity for bare Co3O4 systems, accompanied by a high selectivity in NOx conversion to harmless nitrate species. A preliminary evaluation of De-NOx performances for functionalized systems revealed a direct dependence of the system behavior on the chemical composition, SnO2/Fe2O3 overlayer morphology, and charge transfer events between the single oxide constituents. Taken together, the present results can provide valuable guidelines for the eventual implementation of improved photocatalysts for air purification.

Radical-triggered cross-linking for molecular layer deposition of SiAlCOH hybrid thin films.

Here, we report on a simultaneous growth and radical-initiated cross-linking of a hybrid thin film in a layer-by-layer manner via molecular layer deposition (MLD). The cross-linked film exhibited a self-limiting MLD growth behavior and improved properties like 12% higher film density and enhanced stability compared to the non-cross-linked film.

Black Au-Decorated TiO2 Produced via Laser Ablation in Liquid.

The rational combination of plasmonic and all-dielectric concepts within hybrid nanomaterials provides a promising route toward devices with ultimate performance and extended modalities. Spectral matching of plasmonic and Mie-type resonances for such nanostructures can only be achieved for their dissimilar characteristic sizes, thus making the resulting hybrid nanostructure geometry complex for practical realization and large-scale replication. Here, we produced amorphous TiO2 nanospheres decorated and doped with Au nanoclusters via single-step nanosecond-laser irradiation of commercially available TiO2 nanopowders dispersed in aqueous HAuCl4. Fabricated hybrids demonstrate remarkable light-absorbing properties (averaged value ≈96%) in the visible and near-IR spectral range mediated by bandgap reduction of the laser-processed amorphous TiO2 as well as plasmon resonances of the decorating Au nanoclusters. The findings are supported by optical spectroscopy, electron energy loss spectroscopy, transmission electron microscopy, and electromagnetic modeling. Light-absorbing and plasmonic properties of the produced hybrids were implemented to demonstrate catalytically passive SERS biosensor for identification of analytes at trace concentrations and solar steam generator that permitted to increase water evaporation rate by 2.5 times compared with that of pure water under identical 1 sun irradiation conditions.

Laser Printing of Plasmonic Nanosponges.

Three-dimensional porous nanostructures made of noble metals represent novel class of nanomaterials promising for nonlinear nanooptics and sensors. Such nanostructures are typically fabricated using either reproducible yet time-consuming and costly multi-step lithography protocols or less reproducible chemical synthesis that involve liquid processing with toxic compounds. Here, we combined scalable nanosecond-laser ablation with advanced engineering of the chemical composition of thin substrate-supported Au films to produce nanobumps containing multiple nanopores inside. Most of the nanopores hidden beneath the nanobump surface can be further uncapped using gentle etching of the nanobumps by an Ar-ion beam to form functional 3D plasmonic nanosponges. The nanopores 10-150 nm in diameter were found to appear via laser-induced explosive evaporation/boiling and coalescence of the randomly arranged nucleation sites formed by nitrogen-rich areas of the Au films. Density of the nanopores can be controlled by the amount of the nitrogen in the Au films regulated in the process of their magnetron sputtering assisted with nitrogen-containing discharge gas.

Nondestructive Femtosecond Laser Lithography of Ni Nanocavities by Controlled Thermo-Mechanical Spallation at the Nanoscale.

We present a new approach to femtosecond direct laser writing lithography to pattern nanocavities in ferromagnetic thin films. To demonstrate the concept, we irradiated 300 nm thin nickel films by single intense femtosecond laser pulses through glass substrate. Using a fluence above the ablation threshold, the process is destructive, leading to the formation of an ablation crater. By progressively lowering the laser fluence, the formation of closed spallation cavities below the ablation threshold is achieved. Systematic studies by the electron and optical interferometric microscopies, supported by molecular dynamics simulations, enabled us to gain an understanding of the thermo-mechanical spallation mechanism at the solid-molten interface. We achieved the fabrication of periodic arrangements of closed spallation nanocavities. Due to their topology, closed magnetic nanocavities can support unique couplings of multiple excitations (magnetic, optical, acoustic, spintronic). Thereby, they offer a unique physics playground for emerging fields in magnetism, magneto-photonic, and magneto-acoustic applications.

Ligand-assisted synthesis and cytotoxicity of ZnSe quantum dots stabilized by N-(2-carboxyethyl)chitosans.

Here we report a green synthesis of ZnSe quantum dots (QDs) in aqueous solution of polyampholyte chitosan derivative - N-(2-carboxyethyl)chitosan (CEC) with substitution degrees (DS) from 0.7 to 1.3 and molecular weight (MW) of 40 kDa and 150 kDa. We have shown that the maximum intensity of photoluminescence (PL) is exhibited by ZnSe QDs synthesized in solutions of CEC with DS 1 at Se:Zn molar ratio 1:2.5. The defect-related band was predominant in the PL spectra of ZnSe QDs obtained at room temperature; however, hydrothermal treatment at 80-150 °C during 1-2 h significantly increased contribution of exciton emission to the spectra. Cytotoxicity of ZnSe QDs was investigated by MTT assay using cancer cell lines SKOV-3; SkBr-3; PANC-1; Colon-26 and human embryonic kidney cell line HEK293. Cytotoxicity of ZnSe QDs did not depend on MW or DS of CEC but significantly depended on the cell line, being the lowest for normal human cells HEK293 and breast cancer cell line SKOV-3. The hydrothermally treated ZnSe QDs showed higher toxicity toward both normal and cancer cell lines. Since ZnSe QDs were toxic for most of the investigated cancer cell lines, they cannot be used as inert tracers for bioimaging, but can be promising for further investigation for anticancer therapy.

Modus Operandi of Protective and Anti-icing Mechanisms Underlying the Design of Longstanding Outdoor Icephobic Coatings.

Atmospheric icing has become a global concern due to hazardous consequences of ice accretion on air, land, and sea transport and infrastructure. Icephobic surfaces due to their physicochemical properties facilitate a decrease in ice and snow accumulation under outdoor conditions. However, a serious problem of most superhydrophobic surfaces described in the literature is poor operational durability under harsh corrosive and abrasive loads characteristic of atmospheric operation. Here, we elucidate main surface phenomena determining the anti-icing behavior and show experimentally how different mechanisms contribute to long-term durability. For comprehensive exploitation of those mechanisms, we have applied a recently proposed strategy based on fine-tuning of both laser processing and protocols of deposition of the fluorooxysilanes onto the nanotextured surface. Prolonged outdoor tests evidence that a developed strategy for modification of materials on the nanolevel allows overcoming the main drawbacks of icephobic coatings reported so far and results in resistance to destroying atmospheric impacts.

Metal-chelate sorbents based on carboxyalkylchitosans: Ciprofloxacin uptake by Cu(II) and Al(III)-chelated cryogels of N-(2-carboxyethyl)chitosan.

Here we propose a metal-chelate approach to removal of fluoroquinolones from aqueous solutions using their ability to bind strongly divalent and trivalent metal ions immobilized in a polymer matrix. Metal-affine sorbents for ciprofloxacin uptake have been fabricated via chelation of Cu(II), Al(III), and Fe(III) ions by supermacroporous cryogel of carboxyalkyl chitosan derivative (N-(2-carboxyethyl)chitosan, CEC) cross-linked with hexamethylene diisocyanate in aqeous medium. We have shown that virgin CEC cryogel adsorbed ciprofoxacin in a cationic form via electrostatic interactions at pH > pICEC, but the efficacy of recovery was below 50% and strongly pH-dependent. Modification of CEC cryogel with Cu(II) and Al(III) ions improved the ciprofloxacin (CIP) recovery by up to 98% in the pH range 7-10, the sorption capacity and affinity for CIP of metal-chelate sorbents increased with metal content and reached maximum values of 280 and 390 mg/g for Cu(II) and Al(III)-chelated cryogels, respectively. The metal-chelated CEC cryogels were efficient for ciprofloxacin removal from solutions with environmentally relevant concentration (50 µg/L) and were applicable as monolith sorbents under dynamic conditions.