The Acoustophotoelectric Effect: Efficient Phonon-Photon-Electron Coupling in Zero-Voltage-Biased 2D SnS2 for Broad-Band Photodetection.

Two-dimensional (2D) layered metal dichalcogenides constitute a promising class of materials for photodetector applications due to their excellent optoelectronic properties. The most common photodetectors, which work on the principle of photoconductive or photovoltaic effects, however, require either the application of external voltage biases or built-in electric fields, which makes it challenging to simultaneously achieve high responsivities across broad-band wavelength excitation─especially beyond the material's nominal band gap─while producing low dark currents. In this work, we report the discovery of an intricate phonon-photon-electron coupling─which we term the acoustophotoelectric effect─in SnS2 that facilitates efficient photodetection through the application of 100 MHz order propagating surface acoustic waves (SAWs). This effect not only reduces the band gap of SnS2 but also provides the requisite momentum for indirect band gap transition of the photoexcited charge carriers, to enable broad-band photodetection beyond the visible light range, while maintaining pA-order dark currents─ without the need for any external voltage bias. More specifically, we show in the infrared excitation range that it is possible to achieve up to 8 orders of magnitude improvement in the material's photoresponsivity compared to that previously reported for SnS2-based photodetectors, in addition to exhibiting superior performance compared to most other 2D materials reported to date for photodetection.

Acoustomicrofluidic Defect Engineering and Ligand Exchange in ZIF-8 Metal-Organic Frameworks.

A way through which the properties of metal-organic frameworks (MOFs) can be tuned is by engineering defects into the crystal structure. Given its intrinsic stability and rigidity, however, it is difficult to introduce defects into zeolitic imidazolate frameworks (ZIFs)-and ZIF-8, in particular-without compromising crystal integrity. In this work, it is shown that the acoustic radiation pressure as well as the hydrodynamic stresses arising from the oscillatory flow generated by coupling high frequency (MHz-order) hybrid surface and bulk acoustic waves into a suspension of ZIF-8 crystals in a liquid pressure transmitting medium is capable of driving permanent structural changes in their crystal lattice structure. Over time, the enhancement in the diffusive transport of guest molecules into the material's pores as a consequence is shown to lead to expansion of the pore framework, and subsequently, the creation of dangling-linker and missing-linker defects, therefore offering the possibility of tuning the type and extent of defects engineered into the MOF through the acoustic exposure time. Additionally, the practical utility of the technology is demonstrated for one-pot, simultaneous solvent-assisted ligand exchange under ambient conditions, for sub-micron-dimension ZIF-8 crystals and relatively large ligands-more specifically 2-aminobenzimidazole-without compromising the framework porosity or overall crystal structure.

Recovery of oxidized two-dimensional MXenes through high frequency nanoscale electromechanical vibration.

MXenes hold immense potential given their superior electrical properties. The practical adoption of these promising materials is, however, severely constrained by their oxidative susceptibility, leading to significant performance deterioration and lifespan limitations. Attempts to preserve MXenes have been limited, and it has not been possible thus far to reverse the material's performance. In this work, we show that subjecting oxidized micron or nanometer thickness dry MXene films-even those constructed from nanometer-order solution-dispersed oxidized flakes-to just one minute of 10 MHz nanoscale electromechanical vibration leads to considerable removal of its surface oxide layer, whilst preserving its structure and characteristics. Importantly, electrochemical performance is recovered close to that of their original state: the pseudocapacitance, which decreased by almost 50% due to its oxidation, reverses to approximately 98% of its original value, with good capacitance retention ( ≈ 93%) following 10,000 charge-discharge cycles at 10 A g-1. These promising results allude to the exciting possibility for rejuvenating the material for reuse, therefore offering a more economical and sustainable route that improves its potential for practical translation.

Enhanced Antimicrobial Activity and Low Phytotoxicity of Acoustically Synthesized Large Aspect Ratio Cu-BTC Metal-Organic Frameworks with Exposed Metal Sites.

Metal-organic frameworks (MOFs) have recently been shown to be effective antimicrobial agents, particularly if they comprise pathogenicidal metal ions. Nevertheless, the accessibility of these active metal sites to the pathogen, and hence the MOFs' antimicrobial activity itself, is often poor since the metal nodes are usually embedded deep within its three-dimensional (3D) structure. We show that a unique copper-based (copper(II)-benzene-1,3,5-tricarboxylate) MOF, whose quasi-two-dimensional (quasi-2D) swordlike structure facilitates exposure of the metal ions along its surface, exhibits enhanced antimicrobial properties against three representative plant pathogens: a bacterium (Pseudomonas syringae), a fungus (Fusarium solani), and a virus (Odontoglossum ringspot virus (ORSV)). Such superior antimicrobial activity results in low minimum inhibitory concentrations (MICs)─half that of a commercial pesticide and an eighth of its conventional 3D cubic MOF counterpart (HKUST-1)─and hence low phytotoxicity, which can be attributed to the accessibility of the surface copper sites to the pathogen, thereby facilitating their adhesion and physical contact with the MOF. Additionally, we observed that orchids treated with the quasi-2D MOF showed negligible phytotoxicity and 80% decreased viral load. This work constitutes the first study to demonstrate the antimicrobial properties of this novel MOF against bacterial, fungal, and viral plant pathogens, and the first chemical control of ORSV.

Acoustomicrofluidic Concentration and Signal Enhancement of Fluorescent Nanodiamond Sensors.

Diamond nitrogen-vacancy (NV) centers constitute a promising class of quantum nanosensors owing to the unique magneto-optic properties associated with their spin states. The large surface area and photostability of diamond nanoparticles, together with their relatively low synthesis costs, make them a suitable platform for the detection of biologically relevant quantities such as paramagnetic ions and molecules in solution. Nevertheless, their sensing performance in solution is often hampered by poor signal-to-noise ratios and long acquisition times due to distribution inhomogeneities throughout the analyte sample. By concentrating the diamond nanoparticles through an intense microcentrifugation effect in an acoustomicrofluidic device, we show that the resultant dense NV ensembles within the diamond nanoparticles give rise to an order-of-magnitude improvement in the measured acquisition time. The ability to concentrate nanoparticles under surface acoustic wave (SAW) microcentrifugation in a sessile droplet is, in itself, surprising given the well-documented challenge of achieving such an effect for particles below 1 µm in dimension. In addition to a demonstration of their sensing performance, we thus reveal in this work that the reason why the diamond nanoparticles readily concentrate under the SAW-driven recirculatory flow can be attributed to their considerably higher density and hence larger acoustic contrast compared to those for typical particles and cells for which the SAW microcentrifugation flow has been shown to date.

Acoustomicrofluidic Synthesis of Pristine Ultrathin Ti3C2Tz MXene Nanosheets and Quantum Dots.

The conversion of layered transition metal carbides and/or nitrides (MXenes) into zero-dimensional structures with thicknesses and lateral dimensions of a few nanometers allows these recently discovered materials with exceptional electronic properties to exploit the additional benefits of quantum confinement, edge effects, and large surface area. Conventional methods for the conversion of MXene nanosheets and quantum dots, however, involve extreme conditions such as high temperatures and/or harsh chemicals that, among other disadvantages, lead to significant degradation of the material as a consequence of their oxidation. Herein, we show that the large surface acceleration-on the order of 10 million g's-produced by high-frequency (10 MHz) nanometer-order electromechanical vibrations on a chip-scale piezoelectric substrate is capable of efficiently nebulizing, and consequently dimensionally reducing, a suspension of multilayer Ti3C2Tz (MXene) into predominantly monolayer nanosheets and quantum dots while, importantly, preserving the material from any appreciable oxidation. As an example application, we show that the high-purity MXene quantum dots produced using this room-temperature chemical-free synthesis method exhibit superior performance as electrode materials for electrochemical sensing of hydrogen peroxide compared to the highly oxidized samples obtained through conventional hydrothermal synthesis. The ability to detect concentrations as low as 5 nM is a 10-fold improvement to the best reported performance of Ti3C2Tz MXene electrochemical sensors to date.

Programmable Phototaxis of Metal-Phenolic Particle Microswimmers.

Light-driven directional motion is common in nature but remains a challenge for synthetic microparticles, particularly regarding collective motion on a macroscopic scale. Successfully engineering microparticles with light-driven collective motion could lead to breakthroughs in drug delivery, contaminant sensing, environmental remediation, and artificial life. Herein, metal-phenolic particle microswimmers capable of autonomously sensing and swimming toward an external light source are reported, with the speed regulated by the wavelength and intensity of illumination. These microswimmers can travel macroscopic distances (centimeters) and can remain illuminated for hours without degradation of motility. Experimental and theoretical analyses demonstrate that motion is generated through chemical transformations of the organic component of the metal-phenolic complex. Furthermore, cargos with specific spectral absorption profiles can be loaded into the particles and endow the particle microswimmers with activated motion corresponding to these spectral characteristics. The programmable nature of the light navigation, tunable size of the particles, and versatility of cargo loading demonstrate the versatility of these metal-phenolic particle microswimmers.

Ultrafast, One-Step, Salt-Solution-Based Acoustic Synthesis of Ti3C2 MXene.

The current quest for two-dimensional transition metal carbides and nitrides (MXenes) has been to circumvent the slow, hazardous, and laborious multistep synthesis procedures associated with conventional chemical MAX phase exfoliation. Here, we demonstrate a one-step synthesis method with local Ti3AlC2 MAX to Ti3C2Tz MXene conversion on the order of milliseconds, facilitated by proton production through solution dissociation under megahertz frequency acoustic excitation. These protons combined with fluorine ions from LiF to selectively etch the MAX phase into MXene, whose delamination is aided by the acoustic forcing. These results have important implications for the future applicability of MXenes, which crucially depend on the development of more efficient synthesis procedures. For proof-of-concept, we show that flexible electrodes fabricated by this method exhibit comparable electrochemical performance to that previously reported.

Acoustic cavitation at low gas pressures in PZT-based ultrasonic systems.

The generation of cavitation-free radicals through evanescent electric field and bulk-streaming was reported when micro-volumes of a liquid were subjected to 10 MHz surface acoustic waves (SAW) on a piezoelectric substrate [Rezk et al., J. Phys. Chem. Lett. 2020, 11, 4655-4661; Rezk et al., Adv. Sci. 2021, 8, 2001983]. In the current study, we have tested a similar hypothesis with PZT-based ultrasonic units (760 kHz and 2 MHz) with varying dissolved gas concentrations, by sonochemiluminescence measurement and iodide dosimetry, to correlate radical generation with dissolved gas concentrations. The dissolved gas concentration was adjusted by controlling the over-head gas pressure. Our study reveals that there is a strong correlation between sonochemical activity and dissolved gas concentration, with negligible sonochemical activity at near-vacuum conditions. We therefore conclude that radical generation is dominated by acoustic cavitation in conventional PZT-based ultrasonic reactors, regardless of the excitation frequency.

Acoustofection: High-Frequency Vibrational Membrane Permeabilization for Intracellular siRNA Delivery into Nonadherent Cells.

The internalization of therapeutic molecules into cells-a critical step in enabling a suite of autologous ex vivo gene and cell therapies-is highly regulated by the lipid barrier imposed by the cell membrane. Strategies to increase the efficiency of delivering these exogenous payloads into the cell, while maintaining the integrity of both the therapeutic molecules to be delivered as well as the host cells they are delivered to, are therefore required. This is especially the case for suspension cells that are particularly difficult to transfect. In this work, we show that it is possible to enhance the uptake of short interfering RNA (siRNA) into nonadherent Jurkat and HuT 78 cells with a rapid poration-free method involving high-frequency (MHz order) acoustic excitation. The 2-fold enhancement in gene knockdown is almost comparable with that obtained with conventional nucleofection, which is among the most widely used intracellular delivery methods, but with considerably higher cell viabilities (>91% compared to approximately 76%) owing to the absence of pore formation. The rapid and effective delivery afforded by the platform, together with its low cost and scalability, therefore renders it a potent tool in the cell engineering pipeline.

Submicron Particle and Cell Concentration in a Closed Chamber Surface Acoustic Wave Microcentrifuge.

Preconcentrating particulate and cellular matter for their isolation or detection is often a necessary and critical sample preparation or purification step in many lab-on-a-chip diagnostic devices. While surface acoustic wave (SAW) microcentrifugation has been demonstrated as a powerful means to drive efficient particle concentration, this has primarily been limited to micron dimension particles. When the particle size is around 1 µm or below, studies on SAW microcentrifugation to date have shown that particle ring-like aggregates can only be obtained in contrast to the localized concentrated clusters that are obtained with larger particles. Considering the importance of submicron particles and bioparticles that are common in many real-world samples, we elucidate why previous studies have not been able to achieve the concentration of these smaller particles to completion, and we present a practical solution involving a novel closed chamber configuration that minimizes sample heating and eliminates evaporation to show that it is indeed possible to drive submicron particle and cell concentration down to 200 nm diameters with SAW microcentrifugation over longer durations.

Free Radical Generation from High-Frequency Electromechanical Dissociation of Pure Water.

We reveal a unique mechanism by which pure water can be dissociated to form free radicals without requiring catalysts, electrolytes, or electrode contact by means of high-frequency nanometer-amplitude electromechanical surface vibrations in the form of surface acoustic waves (SAWs) generated on a piezoelectric substrate. The physical undulations associated with these mechanical waves, in concert with the evanescent electric field arising from the piezoelectric coupling, constitute half-wavelength "nanoelectrochemical cells" in which liquid is trapped within the SAW potential minima with vertical dimensions defined by the wave amplitude (∼10 nm), thereby forming highly confined polarized regions with intense electric field strengths that enable the breakdown of water. The ions and free radicals that are generated rapidly electromigrate under the high field intensity in addition to being convectively transported away from the cells by the bulk liquid recirculation generated by the acoustic excitation, thereby overcoming mass transport limitations that lead to ion recombination.

Ultrafast assembly of swordlike Cu3(1,3,5-benzenetricarboxylate)n metal-organic framework crystals with exposed active metal sites.

Owing to their large surface area and high uptake capacity, metal-organic frameworks (MOFs) have attracted considerable attention as potential materials for gas storage, energy conversion, and electrocatalysis. Various strategies have recently been proposed to manipulate the MOF surface chemistry to facilitate exposure of the embedded metal centers at the crystal surface to allow more effective binding of target molecules to these active sites. Nevertheless, such strategies remain complex, often requiring strict control over the synthesis conditions to avoid blocking pore access, reduction in crystal quality, or even collapse of the entire crystal structure. In this work, we exploit the hydrodynamics and capillary resonance associated with acoustically-driven dynamically spreading and nebulizing thin films as a new method for ultrafast synthesis of swordlike Cu3(1,3,5-benzenetricarboxylate)n (Cu-BTC) MOFs with unique monoclinic crystal structures (P21/n) distinct to that obtained via conventional bulk solvothermal synthesis, with 'swordlike' morphologies whose lengths far exceed their thicknesses. Through pulse modulation and taking advantage of the rapid solvent evaporation associated with the high nebulisation rates, we are also able to control the thicknesses of these large aspect ratio (width and length with respect to the thickness) crystals by arresting their vertical growth, which, in turn, allows exposure of the metal active sites at the crystal surface. An upshot of such active site exposure on the crystal surface is the concomitant enhancement in the conductivity of the MOF, evident from the improvement in its current density by two orders of magnitude.

High Frequency Sonoprocessing: A New Field of Cavitation-Free Acoustic Materials Synthesis, Processing, and Manipulation.

Ultrasound constitutes a powerful means for materials processing. Similarly, a new field has emerged demonstrating the possibility for harnessing sound energy sources at considerably higher frequencies (10 MHz to 1 GHz) compared to conventional ultrasound (⩽3 MHz) for synthesizing and manipulating a variety of bulk, nanoscale, and biological materials. At these frequencies and the typical acoustic intensities employed, cavitation-which underpins most sonochemical or, more broadly, ultrasound-mediated processes-is largely absent, suggesting that altogether fundamentally different mechanisms are at play. Examples include the crystallization of novel morphologies or highly oriented structures; exfoliation of 2D quantum dots and nanosheets; polymer nanoparticle synthesis and encapsulation; and the possibility for manipulating the bandgap of 2D semiconducting materials or the lipid structure that makes up the cell membrane, the latter resulting in the ability to enhance intracellular molecular uptake. These fascinating examples reveal how the highly nonlinear electromechanical coupling associated with such high-frequency surface vibration gives rise to a variety of static and dynamic charge generation and transfer effects, in addition to molecular ordering, polarization, and assembly-remarkably, given the vast dimensional separation between the acoustic wavelength and characteristic molecular length scales, or between the MHz-order excitation frequencies and typical THz-order molecular vibration frequencies.

On-Chip Generation of Vortical Flows for Microfluidic Centrifugation.

Microcentrifugation constitutes an important part of the microfluidic toolkit in a similar way that centrifugation is crucial to many macroscopic procedures, given that micromixing, sample preconcentration, particle separation, component fractionation, and cell agglomeration are essential operations in small scale processes. Yet, the dominance of capillary and viscous effects, which typically tend to retard flow, over inertial and gravitational forces, which are often useful for actuating flows and hence centrifugation, at microscopic scales makes it difficult to generate rotational flows at these dimensions, let alone with sufficient vorticity to support efficient mixing, separation, concentration, or aggregation. Herein, the various technologies-both passive and active-that have been developed to date for vortex generation in microfluidic devices are reviewed. Various advantages or limitations associated with each are outlined, in addition to highlighting the challenges that need to be overcome for their incorporation into integrated microfluidic devices.

Fast three-dimensional micropatterning of PC12 cells in rapidly crosslinked hydrogel scaffolds using ultrasonic standing waves.

The ability to spatially organise the microenvironment of tissue scaffolds unlocks the potential of many scaffold-based tissue engineering applications. An example application is to aid the regeneration process of peripheral nerve injuries. Herein, we present a promising approach for three-dimensional (3D) micropatterning of nerve cells in tissue scaffolds for peripheral nerve repair. In particular, we demonstrate the 3D micropatterning of PC12 cells in a gelatin-hydroxyphenylpropionic acid (Gtn-HPA) hydrogel using ultrasound standing waves (USWs). PC12 cells were first aligned in 3D along nodal planes by the USWs in Gtn-HPA hydrogel precursor solution. The precursor was then crosslinked using horseradish peroxidase (HRP) and diluted hydrogen peroxide (H2O2), thus immobilising the aligned cells within 90-120 s. This micropatterning process is cost effective and can be replicated easily without the need for complex and expensive specialised equipment. USW-aligned PC12 cells showed no adverse effect in terms of viability or ability to proliferate. To our best knowledge, this is the first report on the effect of USW alignment on neural cell differentiation. Differentiated and USW-aligned PC12 cells showed directional uniformity after 20 d, making this technique a promising alternative approach to guide the nerve regeneration process.

Rapid dry exfoliation method for tuneable production of molybdenum disulphide quantum dots and large micron-dimension sheets.

Despite advances in two-dimensional (2D) transition metal dichalcogenide research owing to their outstanding physical properties, the synthesis of large micron-dimension single-layer sheets of these materials remains a challenge. Here, we present a novel and unique method to rapidly and flexibly exfoliate bulk molybdenum disulphide (MoS2) into either small nanometre-dimension quantum dots (QDs) or large micron-dimension sheets comprising predominantly single- or few-layers. The exfoliation process is conducted in dry phase, i.e., without liquid, by exploiting nanometer-amplitude MHz-order surface vibrations in the form of surface acoustic waves (SAWs). To produce the small QDs, we take advantage of the unprecedentedly large surface acceleration-on the order of 108 m s-2-to induce an iterative impaction mechanism involving successive ejection and collision of the bulk MoS2 aggregates within a miniature enclosure in order to progressively thin and break their lateral dimensions into single- and few-layer QDs. In contrast, we suppress the impaction in the zero-height enclosure limit by confining the bulk MoS2 under adhesive tape such that the shear that arises due to the travelling SAW on the substrate progressively thins the material whilst preserving their lateral dimension such that large, predominantly-monolayer, micron-sized sheets are produced with high substrate coverage up to around 80%. This fast, additive-free and dry exfoliation platform potentially presents a simple yet scalable micromechanical exfoliation method towards viable commercial production of 2D transition metal dichalcogenides.

Miniaturised acoustofluidic tactile haptic actuator.

Tactile haptic feedback is an important consideration in the design of advanced human-machine interfaces, particularly in an age of increasing reliance on automation and artificial intelligence. In this work, we show that the typical nanometer-order surface displacement amplitudes of piezoelectric transducers-which are too small to be detectable by the human touch, and constitute a significant constraint in their use for tactile haptic surface actuation-can be circumvented by coupling the vibration into a liquid to drive the deflection of a thermoplastic membrane. In particular, transmission of the sound energy from the standing wave vibration generated along a piezoelectric transducer into a microfluidic chamber atop which the membrane is attached is observed to amplify the mechanical vibration signalling through both the acoustic radiation pressure and the viscous normal stress acting on the membrane-the latter arising due to the acoustic streaming generated as the sound wave propagates through the liquid-to produce 100 µm-order static deflections of the membrane, upon which approximately 0.5 µm dynamic vibrations at frequencies around 1 kHz are superimposed; both these static and dynamic responses are within the perception range for human finger sensation. The large static deformation, the relatively fast response time, and the ability to incorporate a dynamic vibrotactile response together with the small size and potential for integration of the device into large scale arrays make this mechanism well suited for driving actuation in devices which require tactile haptic responses.

Acoustomicrofluidic assembly of oriented and simultaneously activated metal-organic frameworks.

The high surface area and porosity, and limitless compound and network combinations between the metal ions and organic ligands making up metal-organic frameworks (MOFs) offer tremendous opportunities for their use in many applications. While numerous methods have been proposed for the synthesis of MOF powders, it is often difficult to obtain oriented crystals with these techniques. Further, the need for additional post-synthesis steps to activate the crystals and release them from the substrate presents a considerable production challenge. Here, we report an acoustically-driven microcentrifugation platform that facilitates fast convective solutal transport, allowing the synthesis of MOF crystals in as short as five minutes. The crystals are not only oriented due to long-range out-of-plane superlattice ordering aided by molecular dipole polarization under the acoustoelectric coupling, but also simultaneously activated during the synthesis process.

Acoustopipetting: Tunable Nanoliter Sample Dispensing Using Surface Acoustic Waves.

We seek to demonstrate a robust, low-cost, and user-friendly acoustomicrofluidic platform that facilitates rapid, reproducible, and precise nanoliter sample dispensing. The solid-state chipscale platform exploits the unprecedented acceleration arising from high-frequency nanoelectromechanical vibrations, on the order of 10 million g, to jet the sample and hence generate a liquid bridge that spans across the substrate, on which the vibrations are generated and from which the sample originates, to a top target plate before rapidly pinching off to deposit the sample on the target with precise and reproducible volumes that can be tuned down to 0.22 µL with a standard error of 6.5% and coefficient of variation of 11.3%. The entire process occurs within approximately 10 ms. In addition to explicating the fundamental physical mechanism that underpins the technology, we demonstrate its use for serial dilution and concentration and, in particular, a cell-based drug toxicology assay. Moreover, we also show that multiple drop dispensing in an array, without requiring repositioning of the chip between dispensing steps, can be achieved through a simple but yet effective sequential directional jetting strategy, therefore allowing significant reduction in the total dispensing time in the case of massive-scale microarray operation. Given its low cost and compact size, the platform can easily be automated and parallelized, thus offering the prospect for introducing large-scale efficiencies in the laboratory workflow.