Ion and Molecular Sieving With Ultrathin Polydopamine Nanomembranes.

In contrast to biological cell membranes, it is still a major challenge for synthetic membranes to efficiently separate ions and small molecules due to their similar sizes in the sub-nanometer range. Inspired by biological ion channels with their unique channel wall chemistry that facilitates ion sieving by ion-channel interactions, the first free-standing, ultrathin (10-17 nm) nanomembranes composed entirely of polydopamine (PDA) are reported here as ion and molecular sieves. These nanomembranes are obtained via an easily scalable electropolymerization strategy and provide nanochannels with various amine and phenolic hydroxyl groups that offer a favorable chemical environment for ion-channel electrostatic and hydrogen bond interactions. They exhibit remarkable selectivity for monovalent ions over multivalent ions and larger species with K+/Mg2+ of ≈4.2, K+/[Fe(CN)6]3- of ≈10.3, and K+/Rhodamine B of ≈273.0 in a pressure-driven process, as well as cyclic reversible pH-responsive gating properties. Infrared spectra reveal hydrogen bond formation between hydrated multivalent ions and PDA, which prevents the transport of multivalent ions and facilitates high selectivity. Chemically rich, free-standing, and pH-responsive PDA nanomembranes with specific interaction sites are proposed as customizable high-performance sieves for a wide range of challenging separation requirements.

Fast Photoactuation and Environmental Response of Humidity-Sensitive pDAP-Silicon Nanocantilevers.

Multi-responsive nanomembranes are a new class of advanced materials that can be harnessed in complex architectures for micro and nano-manipulators, artificial muscles, energy harvesting, soft robotics, and sensors. The design and fabrication of responsive membranes must meet such challenges as trade-offs between responsiveness and mechanical durability, volumetric low-cost production ensuring low environmental impact, and compatibility with standard technologies or biological systems This work demonstrates the fabrication of multi-responsive, mechanically robust poly(1,3-diaminopropane) (pDAP) nanomembranes and their application in fast photoactuators. The pDAP films are developed using a plasma-assisted polymerization technique that offers large-scale production and versatility of potential industrial relevance. The pDAP layers exhibit high elasticity with the Young's modulus of ≈7 GPa and remarkable mechanical durability across 20-80 °C temperatures. Notably, pDAP membranes reveal immediate and reversible contraction triggered by light, rising temperature, or reducing relative humidity underpinned by a reversible water sorption mechanism. These features enable the fabrication of photoactuators composed of pDAP-coated Si nanocantilevers, demonstrating ms timescale response to light, tens of µm deflections, and robust performance up to kHz frequencies. These results advance fundamental research on multi-responsive nanomembranes and hold the potential to boost versatile applications in light-to-motion conversion and sensing toward the industrial level.

Architecture Controls Phonon Propagation in All-Solid Brush Colloid Metamaterials.

Brillouin light scattering and elastodynamic theory are concurrently used to determine and interpret the hypersonic phonon dispersion relations in brush particle solids as a function of the grafting density with perspectives in optomechanics, heat management, and materials metrology. In the limit of sparse grafting density, the phonon dispersion relations bear similarity to polymer-embedded colloidal assembly structures in which phonon dispersion can be rationalized on the basis of perfect boundary conditions, i.e., isotropic stiffness transitions across the particle interface. In contrast, for dense brush assemblies, more complex dispersion characteristics are observed that imply anisotropic stiffness transition across the particle/polymer interface. This provides direct experimental validation of phonon propagation changes associated with chain conformational transitions in dense particle brush materials. A scaling relation between interface tangential stiffness and crowding of polymer tethers is derived that provides a guideline for chemists to design brush particle materials with tailored phononic dispersion characteristics. The results emphasize the role of interfaces in composite materials systems. Given the fundamental relevance of phonon dispersion to material properties such as thermal transport or mechanical properties, it is also envisioned that the results will spur the development of novel functional hybrid materials.

Control of Intermolecular Interactions toward the Production of Free-Standing Interfacial Polydopamine Films.

Aggregation of the polydopamine (PDA) molecular building blocks at the air/water interface leads to obtaining large surface nanometric-thin films. This mechanism follows two possible pathways, namely, covalent or non-covalent self-assembly, which result in a different degree of structure order and, consequently, different structural properties. Control of this mechanism could be vital for applications that require true self-support PDA free-standing films, for example, electrochemical sensing or membrane technology. Here, we are considering the impact of boric acid (BA) and Cu2+ ions on the mentioned mechanism exclusively for the free-standing films from the air/water interface. We have employed and refined our own spectroscopic reflectometry method to achieve an exceptionally high real-time control over the thickness growth. It turned out that BA and Cu2+ ions significantly impact the film growth process. Reduction of the nanoparticles size and their number was examined via UV-vis spectroscopy and transmission electron microscopy, showing a colossal reduction in the mean diameter of nanoparticles in the case of BA and a moderate reduction in the case of Cu2+. This modification is leading to significant enhancement of the process efficiency through moderation of the topological properties of the films, as revealed by atomic force microscopy. Next, applying infrared, Raman, and X-ray photoelectron spectroscopy, we presented small amounts of metal (B or Cu) in the final structure of PDA and simultaneously their vital role in the oxidation mechanism and cross-linking through covalent or non-covalent bonds. Therefore, we revealed the possibility of synthesizing films via the expected self-assembly mechanism which has hitherto been out of control. Moreover, modification of mechanical properties toward exceptionally elastic films through the BA-assisted synthesis pathway was shown by achieving Young's modulus value up to 24.1 ± 5.6 and 18.3 ± 6.4 GPa, using nanoindentation and Brillouin light scattering, respectively.

Photo-elasticity of silk fibroin harnessing whispering gallery modes.

Silk fibroin is an important biomaterial for photonic devices in wearable systems. The functionality of such devices is inherently influenced by the stimulation from elastic deformations, which are mutually coupled through photo-elasticity. Here, we investigate the photo-elasticity of silk fibroin employing optical whispering gallery mode resonation of light at the wavelength of 1550 nm. The fabricated amorphous (Silk I) and thermally-annealed semi-crystalline structure (Silk II) silk fibroin thin film cavities display typical Q-factors of about 1.6 × 104. Photo-elastic experiments are performed tracing the TE and TM shifts of the whispering gallery mode resonances upon application of an axial strain. The strain optical coefficient K' for Silk I fibroin is found to be 0.059 ± 0.004, with the corresponding value for Silk II being 0.129 ± 0.004. Remarkably, the elastic Young's modulus, measured by Brillouin light spectroscopy, is only about 4% higher in the Silk II phase. However, differences between the two structures are pronounced regarding the photo-elastic properties due to the onset of ß-sheets that dominates the Silk II structure.

Fano meets Stokes: Four-order-of-magnitude enhancement of asymmetric Brillouin light scattering spectra.

Observation of Fano resonances in various physical phenomena is usually ascribed to the coupling of discrete states with background continuum, as it has already been reported for various physical phenomena. Here, we report on Fano lineshapes of nonthermal GHz phonons generated and observed with pumped Brillouin light scattering in gold-silicon thin membranes, overlapping the broad zero-shift background of yet questionable origin. The system's broken mid-plane symmetry enabled the generation of coherent quasi-symmetric and quasi-antisymmetric Lamb acoustic waves/phonons, leading to the four orders-of-magnitude enhancement of Brillouin light scattering. Notably, the membrane asymmetry resulted also in the mode-dependent Stokes and anti-Stokes Fano lineshapes asymmetry.

Size-dependent nanoscale soldering of polystyrene colloidal crystals by supercritical fluids.

HYPOTHESIS: Polymer particles self-assembled into colloidal crystals have exciting applications in photonics, phononics, templates for nanolithography, and coatings. Cold soldering utilizing polymer plasticization by supercritical fluids enables a novel, low-cost, low-effort, chemical-free means for uniform mechanical strengthening of fragile polymer colloidal crystals at moderate temperatures. Here, we aim to elucidate the role of particle size and gas-specific response for the most efficient soldering, exploring the full potential of this method. EXPERIMENTS: We investigate the elastic properties of polystyrene colloidal crystals made of nanoparticles with different diameters (143 to 830 nm) upon treatment with supercritical Ar and He at room temperature. By employing Brillouin light scattering, we quantify the effect of nanoparticle size on the strengthening of interparticle contacts, evaluating the permanent change in the effective elastic modulus upon cold soldering. FINDINGS: The relative change in the effective elastic modulus reveals nonmonotonic dependence on the particle size with the most efficient soldering for mid-sized nanoparticles (about 610 nm diameter). We attribute this behavior to the crucial role of intrinsic fabrication impurities, which reduces the nanoparticles' free surface exposed to plasticization by supercritical fluids. Supercritical Ar, a good solvent for polystyrene, enabled effective soldering of nanoparticles, whereas high-pressure He treatment is entirely reversible.

Optomechanical Hot-Spots in Metallic Nanorod-Polymer Nanocomposites.

Plasmonic coupling between adjacent metallic nanoparticles can be exploited for acousto-plasmonics, single-molecule sensing, and photochemistry. Light absorption or electron probes can be used to study plasmons and their interactions, but their use is challenging for disordered systems and colloids dispersed in insulating matrices. Here, we investigate the effect of plasmonic coupling on optomechanics with Brillouin light spectroscopy (BLS) in a prototypical metal-polymer nanocomposite, gold nanorods (Au NRs) in polyvinyl alcohol. The intensity of the light inelastically scattered on thermal phonons captured by BLS is strongly affected by the wavelength of the probing light. When light is resonant with the transverse plasmons, BLS reveals mostly the normal vibrational modes of single NRs. For lower energy off-resonant light, BLS is dominated by coupled bending modes of NR dimers. The experimental results, supported by optomechanical calculations, document plasmonically enhanced BLS and reveal energy-dependent confinement of coupled plasmons close to the tips of NR dimers, generating BLS hot-spots. Our work establishes BLS as an optomechanical probe of plasmons and promotes nanorod-soft matter nanocomposites for acousto-plasmonic applications.

On the origin of elasticity and heat conduction anisotropy of liquid crystal elastomers at gigahertz frequencies.

Liquid crystal elastomers that offer exceptional load-deformation response at low frequencies often require consideration of the mechanical anisotropy only along the two symmetry directions. However, emerging applications operating at high frequencies require all five true elastic constants. Here, we utilize Brillouin light spectroscopy to obtain the engineering moduli and probe the strain dependence of the elasticity anisotropy at gigahertz frequencies. The Young's modulus anisotropy, E||/E⊥~2.6, is unexpectedly lower than that measured by tensile testing, suggesting disparity between the local mesogenic orientation and the larger scale orientation of the network strands. Unprecedented is the robustness of E||/E⊥ to uniaxial load that it does not comply with continuously transformable director orientation observed in the tensile testing. Likewise, the heat conductivity is directional, κ||/κ⊥~3.0 with κ⊥ = 0.16 Wm-1K-1. Conceptually, this work reveals the different length scales involved in the thermoelastic anisotropy and provides insights for programming liquid crystal elastomers on-demand for high-frequency applications.

Origin of the Acoustic Bandgaps in Hypersonic Colloidal Phononics: The Role of the Elastic Impedance.

How phonons propagate in nanostructures determines the flow of elastic and thermal energy in dielectric materials. However, a reliable theoretical prediction of the phonon dispersion relation requires experimental verification both near to and far from the Brillouin zone of the nanostructure. We report on the experimental hypersonic phonon dispersion of hard (SiO2) and soft (polymer) fcc colloidal crystals infiltrated in liquid polydimethylsiloxane with different elastic impedance contrast using Brillouin light spectroscopy. We discuss the distinct differences with first-principles full elastodynamic calculations involving a multiple-scattering theory. Interparticle contacts strongly impact the long-wavelength speed of sound and the nature of the particle vibration resonance-induced hybridization hypersonic bandgap. The absence of the order-induced Bragg bandgap in SiO2 and its presence in soft opals cannot be fully accounted for by the theory, limiting its predictive power. Bridging the elasticity of the two colloidal crystals with suitable SiO2 core-shell (polymer) particles reveals an unprecedented crossover behavior in the dispersion relation. In view of many conversational parameters, the control tuning of phonon propagation in soft matter-based hypersonic phononics remains challenging.

Fast Light-Driven Motion of Polydopamine Nanomembranes.

The actuation of micro- and nanostructures controlled by external stimuli remains one of the exciting challenges in nanotechnology due to the wealth of fundamental questions and potential applications in energy harvesting, robotics, sensing, biomedicine, and tunable metamaterials. Photoactuation utilizes the conversion of light into motion through reversible chemical and physical processes and enables remote and spatiotemporal control of the actuation. Here, we report a fast light-to-motion conversion in few-nanometer thick bare polydopamine (PDA) membranes stimulated by visible light. Light-induced heating of PDA leads to desorption of water molecules and contraction of membranes in less than 140 µs. Switching off the light leads to a spontaneous expansion in less than 20 ms due to heat dissipation and water adsorption. Our findings demonstrate that pristine PDA membranes are multiresponsive materials that can be harnessed as robust building blocks for soft, micro-, and nanoscale actuators stimulated by light, temperature, and moisture level.

Self-Aligned Bilayers for Flexible Free-Standing Organic Field-Effect Transistors.

Free-standing and flexible field-effect transistors based on 6,13-bis(triisopropylsilylethynyl)-pentacene (TIPS-pentacene)/polystyrene bilayers are obtained by well-controlled phase separation of both components. The phase separation is induced by solvent vapor annealing of initially amorphous blend films, leading to crystallization of TIPS-pentacene as the top layer. The crystallinity and blend morphology strongly depend on the molecular weight of polystyrene, and under optimized conditions, distinct phase separation with a well-defined and trap-free interface between both fractions is achieved. Due to the distinct bilayer morphology, the resulting flexible field-effect transistors reveal similar charge carrier mobilities as rigid devices and additionally pronounced environmental and bias stress stabilities. The performance of the flexible transistors remains stable up to a strain of 1.8%, while above this deformation, a close relation between current and strain is observed that is required for applications in strain sensors.

Influence of Surfactant-Mediated Interparticle Contacts on the Mechanical Stability of Supraparticles.

Colloidal supraparticles are micron-scale spherical assemblies of uniform primary particles, which exhibit emergent properties of a colloidal crystal, yet exist as a dispersible powder. A prerequisite to utilize these emergent functionalities is that the supraparticles maintain their mechanical integrity upon the mechanical impacts that are likely to occur during processing. Understanding how the internal structure relates to the resultant mechanical properties of a supraparticle is therefore of general interest. Here, we take the example of supraparticles templated from water/fluorinated oil emulsions in droplet-based microfluidics and explore the effect of surfactants on their mechanical properties. Stable emulsions can be generated by nonionic block copolymers consisting of a hydrophilic and fluorophilic block and anionic fluorosurfactants widely available under the brand name Krytox. The supraparticles formed in the presence of both types of surfactants appear structurally similar, but differ greatly in their mechanical properties. While the nonionic surfactant induces superior mechanical stability and ductile fracture behavior, the anionic Krytox surfactant leads to weak supraparticles with brittle fracture. We complement this macroscopic picture with Brillouin light spectroscopy that is very sensitive to the interparticle contacts for subnanometer-thick adsorbed layers atop of the nanoparticle. While the anionic Krytox does not significantly affect the interparticle bonds, the amphiphilic nonionic surfactant drastically strengthens these bonds to the point that individual particle vibrations are not resolved in the experimental spectrum. Our results demonstrate that seemingly subtle changes in the physicochemical properties of supraparticles can drastically impact the resultant mechanical properties.

Thickness-Dependent Elastic Softening of Few-Layer Free-Standing MoSe2.

Few-layer van der Waals (vdW) materials have been extensively investigated in terms of their exceptional electronic, optoelectronic, optical, and thermal properties. Simultaneously, a complete evaluation of their mechanical properties remains an undeniable challenge due to the small lateral sizes of samples and the limitations of experimental tools. In particular, there is no systematic experimental study providing unambiguous evidence on whether the reduction of vdW thickness down to few layers results in elastic softening or stiffening with respect to the bulk. In this work, micro-Brillouin light scattering is employed to investigate the anisotropic elastic properties of single-crystal free-standing 2H-MoSe2 as a function of thickness, down to three molecular layers. The so-called elastic size effect, that is, significant and systematic elastic softening of the material with decreasing numbers of layers is reported. In addition, this approach allows for a complete mechanical examination of few-layer membranes, that is, their elasticity, residual stress, and thickness, which can be easily extended to other vdW materials. The presented results shed new light on the ongoing debate on the elastic size-effect and are relevant for performance and durability of implementation of vdW materials as resonators, optoelectronic, and thermoelectric devices.

Frequency-domain study of nonthermal gigahertz phonons reveals Fano coupling to charge carriers.

Telecommunication devices exploit hypersonic gigahertz acoustic phonons to mediate signal processing with microwave radiation, and charge carriers to operate various microelectronic components. Potential interactions of hypersound with charge carriers can be revealed through frequency- and momentum-resolved studies of acoustic phonons in photoexcited semiconductors. Here, we present an all-optical method for excitation and frequency-, momentum-, and space-resolved detection of gigahertz acoustic waves in a spatially confined model semiconductor. Lamb waves are excited in a bare silicon membrane using femtosecond optical pulses and detected with frequency-domain micro-Brillouin light spectroscopy. The population of photoexcited gigahertz phonons displays a hundredfold enhancement as compared with thermal equilibrium. The phonon spectra reveal Stokes-anti-Stokes asymmetry due to propagation, and strongly asymmetric Fano resonances due to coupling between the electron-hole plasma and the photoexcited phonons. This work lays the foundation for studying hypersonic signals in nonequilibrium conditions and, more generally, phonon-dependent phenomena in photoexcited nanostructures.

Mechanical reinforcement of polymer colloidal crystals by supercritical fluids.

Colloidal crystals realized by self-assembled polymer nanoparticles have prominent attraction as a platform for various applications from assembling photonic and phononic crystals, acoustic metamaterials to coating applications. However, the fragility of these systems limits their application horizon. In this work the uniform mechanical reinforcement and tunability of 3D polystyrene colloidal crystals by means of cold soldering are reported. This structural strengthening is achieved by high pressure gas (N2 or Ar) plasticization at temperatures well below the glass transition. Brillouin light scattering is employed to monitor in-situ the mechanical vibrations of the crystal and thereby determine preferential pressure, temperature and time ranges for soldering, i.e. formation of physical bonding among the nanoparticles while maintaining the shape and translational order. This low-cost method is potentially useful for fabrication and tuning of durable devices including applications in photonics, phononics, acoustic metamaterials, optomechanics, surface coatings and nanolithography.

Multiband Hypersound Filtering in Two-Dimensional Colloidal Crystals: Adhesion, Resonances, and Periodicity.

The hypersonic phonon propagation in large-area two-dimensional colloidal crystals is probed by spontaneous micro Brillouin light scattering. The dispersion relation of thermally populated Lamb waves reveals multiband filtering due to three distinct types of acoustic band gaps. We find Bragg gaps accompanied by two types of hybridization gaps in both sub- and superwavelength regimes resulting from contact-based resonances and nanoparticle eigenmodes, respectively. The operating GHz frequencies can be tuned by particle size and depend on the adhesion at the contact interfaces. The experimental dispersion relations are well represented by a finite element method model enabling identification of observed modes. The presented approach also allows for contactless study of the contact stiffness of submicrometer particles, which reveals size effect deviating from macroscopic predictions.

Shell Architecture Strongly Influences the Glass Transition, Surface Mobility, and Elasticity of Polymer Core-Shell Nanoparticles.

Despite the growing application of nanostructured polymeric materials, there still remains a large gap in our understanding of polymer mechanics and thermal stability under confinement and near polymer-polymer interfaces. In particular, the knowledge of polymer nanoparticle thermal stability and mechanics is of great importance for their application in drug delivery, phononics, and photonics. Here, we quantified the effects of a polymer shell layer on the modulus and glass-transition temperature (T g) of polymer core-shell nanoparticles via Brillouin light spectroscopy and modulated differential scanning calorimetry, respectively. Nanoparticles consisting of a polystyrene (PS) core and shell layers of poly(n-butyl methacrylate) (PBMA) were characterized as model systems. We found that the high T g of the PS core was largely unaffected by the presence of an outer polymer shell, whereas the lower T g of the PBMA shell layer decreased with increasing PBMA thickness. The surface mobility was revealed at a temperature about 15 K lower than the T g of the PBMA shell layer. Overall, the modulus of the core-shell nanoparticles decreased with increasing PBMA shell layer thickness. These results suggest that the nanoparticle modulus and T g can be tuned independently through the control of nanoparticle composition and architecture.

Thermal conductivity in disordered porous nanomembranes.

In this work we study the effects of disorder on the thermal conductivity of porous 100 nm thick silicon membranes, in which the size, shape and position of the pores were varied randomly. Measurements using two-laser Raman thermometry on both non-patterned and porous membranes revealed more than a 10-fold reduction of the thermal conductivity compared to that of bulk silicon and a six-fold reduction compared to non-patterned membranes for the sample with random pore shapes. Using Monte Carlo methods we solved the Boltzmann transport equation for phonons and compared different possibilities of pore organization and its influence on the thermal conductivity of the samples. The simulations confirmed that the strongest reduction of thermal conductivity is achieved for a distribution of pores with arbitrary shapes that partially overlap. Up to a 15% reduction of the thermal conductivity with respect to the purely circular pores was predicted for a porous membrane with 37% filling fraction. The effect of the pore shape and distribution was further studied. Maps of temperature and heat flux distributions clearly showed that for particular pore placement heat transport can be efficiently blocked and hot spots can be found in narrow channels between pores. These findings have an impact on the fabrication of membrane-based thermoelectric devices, where low thermal conductivity is required. This work shows that for porous membranes with a given filling fraction the thermal conductivity can be further modified by introducing disorder in the shape and placement of the pores.

Direct observation of polymer surface mobility via nanoparticle vibrations.

Measuring polymer surface dynamics remains a formidable challenge of critical importance to applications ranging from pressure-sensitive adhesives to nanopatterning, where interfacial mobility is key to performance. Here, we introduce a methodology of Brillouin light spectroscopy to reveal polymer surface mobility via nanoparticle vibrations. By measuring the temperature-dependent vibrational modes of polystyrene nanoparticles, we identify the glass-transition temperature and calculate the elastic modulus of individual nanoparticles as a function of particle size and chemistry. Evidence of surface mobility is inferred from the first observation of a softening temperature, where the temperature dependence of the fundamental vibrational frequency of the nanoparticles reverses slope below the glass-transition temperature. Beyond the fundamental vibrational modes given by the shape and elasticity of the nanoparticles, another mode, termed the interaction-induced mode, was found to be related to the active particle-particle adhesion and dependent on the thermal behavior of nanoparticles.