Phononic crystal structures for acoustically driven microfluidic manipulations

The development of microfluidic systems is often constrained both by difficulties associated with the chip interconnection to other instruments and by limitations imposed by the mechanisms that can enable fluid movement and processing. Surface acoustic wave (SAW) devices have shown promise in allowing samples to be manipulated, although designing complex fluid operations involves using multiple electrode transducers. We now demonstrate a simple interface between a piezoelectric SAW device and a disposable microfluidic chip, patterned with phononic structures to control the acoustic wave propagation. The surface wave is coupled from the piezoelectric substrate into the disposable chip where it interacts with the phononic lattice. By implementing both a phononic filter and an acoustic waveguide, we illustrate the potential of the technique by demonstrating microcentrifugation for particle and cell concentration in microlitre droplets. We show for the first time that the interaction of the fluid within this metamaterial phononic lattice is dependent upon the frequency of the acoustic wave, providing a route to programme complex fluidic functions into a microchip (in much the same way, by analogy, that a holographic element would change the phase of a light wave in optical tweezers). A practical realisation of this involves the centrifugation of blood on the chip.     

Optimizing the quasi-equilibrium state of hot carriers in all-inorganic lead halide perovskite nanocrystals through Mn doping: fundamental dynamics and device perspectives

Hot carrier (HC) cooling accounts for the significant energy loss in lead halide perovskite (LHP) solar cells. Here, we study HC relaxation dynamics in Mn-doped LHP CsPbI₃ nanocrystals (NCs), combining transient absorption spectroscopy and density functional theory (DFT) calculations. We demonstrate that Mn²⁺ doping (1) enlarges the longitudinal optical (LO)–acoustic phonon bandgap, (2) enhances the electron–LO phonon coupling strength, and (3) adds HC relaxation pathways via Mn orbitals within the bands. The spectroscopic study shows that the HC cooling process is decelerated after doping under band-edge excitation due to the dominant phonon bandgap enlargement. When the excitation photon energy is larger than the optical bandgap and the Mn²⁺ transition gap, the doping accelerates the cooling rate owing to the dominant effect of enhanced carrier–phonon coupling and relaxation pathways. We demonstrate that such a phenomenon is optimal for the application of hot carrier solar cells. The enhanced electron–LO phonon coupling and accelerated cooling of high-temperature hot carriers efficiently establish a high-temperature thermal quasi-equilibrium where the excessive energy of the hot carriers is transferred to heat the cold carriers. On the other hand, the enlarged phononic band-gap prevents further cooling of such a quasi-equilibrium, which facilitates the energy conversion process. Our results manifest a straightforward methodology to optimize the HC dynamics for hot carrier solar cells by element doping.

Mn doping modulates the hot carrier dynamics in all-inorganic lead halide perovskite nanocrystals according to the excitation energy.     

Surface vibration induced spatial ordering of periodic polymer patterns on a substrate

We demonstrate the possibility of producing regular, long-range, spatially ordered polymer patterns without requiring the use of physical or chemical templating through the interfacial destabilization of a thin polymer film driven by surface acoustic waves (SAWs). The periodicity and spot size of the pattern are observed to be dependent on a single parameter, that is, the SAW frequency (or wavelength), therefore offering a rapid, simple, yet novel method for self-organized regular spatial polymer pattern formation that is far more tunable than conventional polymer patterning procedures.     

Integrated immunoassay using tuneable surface acoustic waves and lensfree detection

The diagnosis of infectious diseases in the Developing World is technologically challenging requiring complex biological assays with a high analytical performance, at minimal cost. By using an opto-acoustic immunoassay technology, integrating components commonly used in mobile phone technologies, including surface acoustic wave (SAW) transducers to provide pressure driven flow and a CMOS camera to enable lensfree detection technique, we demonstrate the potential to produce such an assay. To achieve this, antibody functionalised microparticles were manipulated on a low-cost disposable cartridge using the surface acoustic waves and were then detected optically. Our results show that the biomarker, interferon-γ, used for the diagnosis of diseases such as latent tuberculosis, can be detected at pM concentrations, within a few minutes (giving high sensitivity at a minimal cost).     

Tritoroidal particle rings formation in open microfluidics induced by standing surface acoustic waves

In this paper, the particle movements in a sessile droplet induced by standing surface acoustic waves (SSAWs) are studied. Tritoroidal particle rings are formed under the interaction of acoustic field and electric field. The experimental results demonstrate that the electric field plays an important role in patterning nanoparticles. The electric field can define the droplet shape due to electrowetting. When the droplet approximates a hemisphere, the acoustic radiation force induced by SSAWs drives the particles to form tritoroidal particle rings. When the droplet approximates a convex plate, the drag force induced by acoustic steaming drives the particle to move. The results will be useful for better understanding the nanoparticle movements in a sessile droplet, which is important to explain the mechanism that SSAWs enhance reaction and crystallization in droplet.     

Employing a cylindrical single crystal in gas-surface dynamics

We describe the use of a polished, hollow cylindrical nickel single crystal to study effects of step edges on adsorption and desorption of gas phase molecules. The crystal is held in an ultra-high vacuum apparatus by a crystal holder that provides axial rotation about a [100] direction, and a crystal temperature range of 89 to 1100 K. A microchannel plate-based low energy electron diffraction/retarding field Auger electron spectrometer (AES) apparatus identifies surface structures present on the outer surface of the cylinder, while a separate double pass cylindrical mirror analyzer AES verifies surface cleanliness. A supersonic molecular beam, skimmed by a rectangular slot, impinges molecules on a narrow longitudinal strip of the surface. Here, we use the King and Wells technique to demonstrate how surface structure influences the dissociation probability of deuterium at various kinetic energies. Finally, we introduce spatially-resolved temperature programmed desorption from areas exposed to the supersonic molecular beam to show how surface structures influence desorption features.     

Roughness-induced acoustic second-harmonic generation during electrochemical metal deposition on the quartz-crystal microbalance

This paper reports on the relation between the surface roughness and emission of compressional waves from the surface of an electrochemical quartz-crystal microbalance. The detection of the compressional waves took place with an ultrasonic microphone and the quartz crystal itself. As a model process, the electrochemical deposition of copper from an acidic copper sulfate solution has been chosen. For this system, the roughness of the layer can be tuned via the current density. Roughness may be a source of the longitudinal waves at twice the frequency of the exciting shear wave (acoustic second-harmonic generation, ASHG) if the flow profile above the quartz-crystal surface is not entirely laminar. Slight deviations from the laminar flow can be reached at high amplitudes of oscillation. Comparing the ASHG efficiency of a rough and smooth surface, we find that the rough surface is more efficient in generating second-harmonic waves. This suggests that ASHG can be used to obtain a roughness parameter independent from the resonance frequency or bandwidth (damping) of a quartz-crystal resonator. Such an independent determination of roughness should be very interesting in practical applications.     

Love waves in SiO(2) layers on STW-resonators based on LiTaO(3)

We present first studies of sensitivity increase of commercially available Murata SAF 380-type surface acoustic wave (SAW) devices by the excitation of Love waves. Sputtered SiO₂ is studied as wave-guiding layer. Excitation of Love waves on such devices is investigated both theoretically and experimentally. It is demonstrated that the application of an optimized wave-guiding layer increases the sensitivity. Both theoretical predictions and experiments yield an optimum layer thickness for maximum mass sensitivity between 3 and 4 μm for the given system.     

Hypersonic acoustic excitations in binary colloidal crystals: big versus small hard sphere control

The phononic band structure of two binary colloidal crystals, at hypersonic frequencies, is studied by means of Brillouin light scattering and analyzed in conjunction with corresponding dispersion diagrams of the single colloidal crystals of the constituent particles. Besides the acoustic band of the average medium, the authors' results show the existence of narrow bands originating from resonant multipole modes of the individual particles as well as Bragg-type modes due to the (short-range) periodicity. Strong interaction, leading to the occurrence of hybridization gaps, is observed between the acoustic band and the band of quadrupole modes of the particles that occupy the largest fractional volume of the mixed crystal; the effective radius is either that of the large (in the symmetric NaCl-type crystalline phase) or the small (in the asymmetric NaZn(13)-type crystalline phase) particles. The possibility to reveal a universal behavior of the phononic band structure for different single and binary colloidal crystalline suspensions, by representing in the dispersion diagrams reduced quantities using an appropriate length scale, is discussed.     

Plasmonic response of ordered arrays of gold nanorods immersed within a nematic liquid crystal

We study theoretically the optical properties of a two-dimensional lattice of metallic (gold) nanorods immersed within a nematic liquid crystal (NLC) strongly anchored to the surface of the nanorods. The distribution of the director field of the NLC is found by minimising the corresponding total free energy via simulated annealing. Optical properties such as transmittance, reflectance and absorbance of the structure are found by employing a hybrid discrete-dipole approximation/layer-multiple-scattering technique. We show, in particular, that when the NLC is strongly anchored to the nanorods, light absorbance is more efficient compared to the case where the liquid crystal (LC) is aligned by application of an external field. Also, the alignment of the LC molecules via an external field leads to a significant shift of the surface-plasmon resonance of the gold nanorods relative to the strong-anchoring case, an effect which can be exploited in switching applications. We also report that the rate of light absorption is a non-monotonic function of the height of nanorods due to the guiding of EM waves taking place for long enough nanorods.     

Solvent-resistant ultraflat gold using liquid glass

Templating against atomically flat materials allows creation of smooth metallic surfaces. The process of adding the backing (superstrate) to the deposited metals has proven to be the most difficult part in producing reliable, large-area, solvent-resistant substrates and has been the subject of recent research. In this paper we describe a simple and inexpensive liquid glass template-stripping (lgTS) method for the fabrication of large area ultraflat gold surfaces. Using our lgTS method, ultraflat gold surfaces with normals aligned along the <111> crystal plane and with a root-mean-square roughness of 0.275 nm (over 1 μm(2)) were created. The surfaces are fabricated on silica-based substrates which are highly solvent resistant and electrically insulating using silicate precursor solution (commonly known as "liquid glass") and concomitant mild heat treatment. We demonstrate the capabilities of such ultraflat gold surfaces by imaging nanoscale objects on top and fabricating microelectrodes as an example application. Because of the simplicity and versatility of the fabrication process, lgTS will have wide-ranging application in imaging, catalysis, electrochemistry, and surface science.     

Phoxonic crystals—a new platform for chemical and biochemical sensors

A new sensor platform is based on so-called phoxonic crystals. Phoxonic crystals are structures designed for simultaneous control of photon and phonon propagation and interaction. They are characterized by a periodic spatial modulation of the dielectric constant as well as elastic properties on a common wavelength scale. Multiple scattering of photons and phonons results in a band gap where propagation of both waves is prohibited. The existence of photonic and phononic band gaps opens up opportunities for novel devices and functional materials. The usage of defect modes is an advantageous concept for measurement. The defect also acts as point of measurement. We show theoretically that the properties of the defect mode can be tailored to provide very high sensitivity to optical and acoustic properties of matter confined within a defect cavity or surrounding the defect or being adsorbed at the cavity surface. In this paper, we introduce the sensor platform and analyze the key features of the sensor transduction scheme. Experimental investigations using a macroscopic device support the theoretical findings.     

Transportation of a microdroplet on an oriented liquid crystal surface

Wetting phenomena play important roles in several technological applications and in many physical and biological thin‐film phenomena, such as wetting, adhesion and friction. One of key issues of these studies is to control the surface energy (or wettability) dynamically for liquid transportation. We have developed a liquid crystal (LC) surface for use as a transport substrate since we expected that the surface energy of an LC surface can be controlled rapidly using an electric field. The rapid control of the polarisability (or wettability) of a liquid crystalline surface by an electric field has been demonstrated, together with the transportation of a liquid microdroplet.     

A simplified measurement procedure and portable electronic photometer for disposable sensors based on ionophore-chromoionophore chemistry for potassium determination

A field-portable photometer for potassium determination with disposable sensors has been developed. It can be applied to routine water and beverage analysis. The disposable sensor is based on ionophore-chromoionophore chemistry. A colour change in the sensing film is detected by measuring the transmitted intensity with a solid state photodetector. Optical excitation at 660 nm is emitted by a light-emitting diode (LED). Negative feedback for LED bias and thermal correction were included to improve system stability. Additionally, a measurement procedure is presented, characterized and validated for in situ photometer use and real-time results. This simplified procedure is based on prior preparation of the disposable sensor in its acidic form and on the use of an absorbance ratio as analytical parameter. The only requirement for analysis is prior equilibration with a buffered sample solution for 3 min and absorbance measurement before and after equilibration. Good sensitivity in the concentration range 5 μM to 100 mM and very good repetitively and stability were achieved that are comparable to those obtained with bulkier analytical instrumentation. Given the compact size, low weight, rapid response and low energy requirement of the electronic photometer developed here, this measurement system is suitable for potassium determination in the field.     

Reduction of threshold of acousto-optic effect in a nematic crystal subject to combined actions

The acousto-optic effect in a homeotropically aligned layer of a nematic liquid crystal was investigated subject to combined actions: 1, for coherent excitation of ultrasonic and viscous waves, 2, for ultrasonic action in an electric field near the Freedericksz transition. The acousto-optic effect threshold was reduced by two orders of magnitude. The experimental results are discussed using the facoustic streaming model. The theoretical analysis is supported by our experimental results.     

A simple model of photoinduced lattice instability

A simple model is developed to describe lattice distortions following photon absorption by a molecular crystal. For excitation localised on the vibrational time scale, the classical motion of a one-dimensional lattice with realistic nearest neighbour interactions is examined. The lattice structure is initially unstable and relaxes via two competing mechanisms: one leads directly to a new symmetric equilibrium, the other produces an intermediate metastable asymmetric lattice structure. This second structure is a possible precursor to excimer formation and photochemical reaction. We present algebraic and numerical analyses to demonstrate that the phonon distribution before excitation determines the dominant relaxation mechanism. In this model, acoustic phonon modes near the zone boundary promote the excimer-like distortion.     

Parahydrogen‐Induced Radio Amplification by Stimulated Emission of Radiation

Radio amplification by stimulated emission of radiation (RASER) was recently discovered in a low‐field NMR spectrometer incorporating a highly specialized radio‐frequency resonator, where a high degree of proton‐spin polarization was achieved by reversible parahydrogen exchange. RASER activity, which results from the coherent coupling between the nuclear spins and the inductive detector, can overcome the limits of frequency resolution in NMR. Here we show that this phenomenon is not limited to low magnetic fields or the use of resonators with high‐quality factors. We use a commercial bench‐top 1.4 T NMR spectrometer in conjunction with pairwise parahydrogen addition producing proton‐hyperpolarized molecules in the Earth's magnetic field (ALTADENA condition) or in a high magnetic field (PASADENA condition) to induce RASER without any radio‐frequency excitation pulses. The results demonstrate that RASER activity can be observed on virtually any NMR spectrometer and measures most of the important NMR parameters with high precision.     

The role of large conformational changes in efficient ultrafast internal conversion: deviations from the energy gap law

Conversion of electronic excitation energy into vibrational energy was investigated for photochromic spiropyran molecules, using femtosecond UV-mid-IR pump-probe spectroscopy. We observe a weaker energy gap dependence than demanded by the "energy gap law". We demonstrate that large conformational changes accompanying the optical excitation can explain the observed time scale and energy gap dependence of ultrafast S(1) --> S(0) internal conversion processes. The possibility of dramatic deviations from standard energy gap law behavior is predicted. We conclude that controlling molecular conformations by rigid environments can have a substantial impact on photophysical and (bio)chemical processes.     

Electrochemistry of zeolites on thickness shear mode oscillators

This paper describes electrochemical studies of thickness shear mode (TSM) acoustic wave oscillators coated with zeolites. The frequency response of gold on AT-cut 9 MHz quartz oscillators of silver-ion-exchanged zeolite-modified electrodes (ZMEs) under an electrochemical bias is interpreted. This is achieved using a combination of cyclic voltammetry, double-potential-step chronocoulometry (DPSC), and the frequency and resistance responses of the quartz crystal oscillators. Three ZMEs were investigated including fully exchanged Ag(12)A plus partially exchanged Ag(6.4)A and Ag(3.5)A. In all cases, the frequency response of the quartz crystal nanobalance (QCN) could only be interpreted when motional resistance changes were considered. This determines the importance of energy storage and energy dissipation of the shear wave produced by the oscillator in the zeolite film, which was affected by the deposition of silver at the zeolite-electrode-solution interface. The silver deposit formed via the reduction of silver ions originally within the zeolite phase mechanically couples the zeolite film to the underlying substrate. The resistance changes occurring during redox are thus linked to an inner interfacial slip between the zeolite film and the underlying oscillating surface. The data presented are consistent with an extrazeolite redox mechanism.     

Design of new integrated optical substrates for immuno-analytical applications

Integrated optical Mach-Zehnder interferometers supply information on changes in refractive index and/or thickness of a film placed as a superstrate on top of one of its surface wave-guides. The internal propagation of light is influenced by the evanescent field reaching into the superstrate. This propagating light interferes with an uninfluenced wave in the second arm after recombination. The result is an intensity modulation depending on the refractive index parameters of the substrate, the waveguide itself and the properties of the superstrate. Taking an antigen layer as the superstrate, its interaction with antibodies changes its thickness by several nanometers. This can be observed by recording the change in intensity of the signal of the interferometer. The sensitivity of such a device depends on particular values of the optical parameters of substrate and waveguide with respect to the given superstrate properties. Computer calculations help to select optimum glass and waveguide fabrication conditions. The numerical results of a variety of assumed conditions have been tested experimentally. The application to the improved detection of triazines is discussed.