Sensitivity of resonance properties of all-dielectric multilayers driven by statistical fluctuations.

In photonics and emerging fields of quantum and topological materials, increasing demands are placed upon the state and control of electromagnetic fields. Dielectric multilayer materials may be designed and optimized to possess extremely sharp spectral and angular photonic resonances allowing for the creation of fields orders of magnitude larger than the exciting field. With enhancements of 104 and higher, the extreme nature of these resonances places high constraints on the statistical properties of the physical and optical characteristics of the materials. To what extent the spectral and angular shifts occur as a result of fluctuations in the refractive indices and morphologies of the involved low-loss subdomains have not been considered previously. Here, we present how parameter variations such as those caused by fluctuations in deposition rate, yielding bias, random and compensated errors, may affect the resonance properties of low-loss all-dielectric stacks.

Plasticity, elasticity, and adhesion energy of plant cell walls: nanometrology of lignin loss using atomic force microscopy.

The complex organic polymer, lignin, abundant in plants, prevents the efficient extraction of sugars from the cell walls that is required for large scale biofuel production. Because lignin removal is crucial in overcoming this challenge, the question of how the nanoscale properties of the plant cell ultrastructure correlate with delignification processes is important. Here, we report how distinct molecular domains can be identified and how physical quantities of adhesion energy, elasticity, and plasticity undergo changes, and whether such quantitative observations can be used to characterize delignification. By chemically processing biomass, and employing nanometrology, the various stages of lignin removal are shown to be distinguished through the observed morphochemical and nanomechanical variations. Such spatially resolved correlations between chemistry and nanomechanics during deconstruction not only provide a better understanding of the cell wall architecture but also is vital for devising optimum chemical treatments.

Opto-nanomechanical spectroscopic material characterization.

The non-destructive, simultaneous chemical and physical characterization of materials at the nanoscale is an essential and highly sought-after capability. However, a combination of limitations imposed by Abbe diffraction, diffuse scattering, unknown subsurface, electromagnetic fluctuations and Brownian noise, for example, have made achieving this goal challenging. Here, we report a hybrid approach for nanoscale material characterization based on generalized nanomechanical force microscopy in conjunction with infrared photoacoustic spectroscopy. As an application, we tackle the outstanding problem of spatially and spectrally resolving plant cell walls. Nanoscale characterization of plant cell walls and the effect of complex phenotype treatments on biomass are challenging but necessary in the search for sustainable and renewable bioenergy. We present results that reveal both the morphological and compositional substructures of the cell walls. The measured biomolecular traits are in agreement with the lower-resolution chemical maps obtained with infrared and confocal Raman micro-spectroscopies of the same samples. These results should prove relevant in other fields such as cancer research, nanotoxicity, and energy storage and production, where morphological, chemical and subsurface studies of nanocomposites, nanoparticle uptake by cells and nanoscale quality control are in demand.

Karhunen-Loève treatment to remove noise and facilitate data analysis in sensing, spectroscopy and other applications.

Resolving weak spectral variations in the dynamic response of materials that are either dominated or excited by stochastic processes remains a challenge. Responses that are thermal in origin are particularly relevant examples due to the delocalized nature of heat. Despite its inherent properties in dealing with stochastic processes, the Karhunen-Loève expansion has not been fully exploited in measurement of systems that are driven solely by random forces or can exhibit large thermally driven random fluctuations. Here, we present experimental results and analysis of the archetypes (a) the resonant excitation and transient response of an atomic force microscope probe by the ambient random fluctuations and nanoscale photothermal sample response, and (b) the photothermally scattered photons in pump-probe spectroscopy. In each case, the dynamic process is represented as an infinite series with random coefficients to obtain pertinent frequency shifts and spectral peaks and demonstrate spectral enhancement for a set of compounds including the spectrally complex biomass. The considered cases find important applications in nanoscale material characterization, biosensing, and spectral identification of biological and chemical agents.

From surface to intracellular non-invasive nanoscale study of living cells impairments.

Among the enduring challenges in nanoscience, subsurface characterization of living cells holds major stakes. Developments in nanometrology for soft matter thriving on the sensitivity and high resolution benefits of atomic force microscopy have enabled detection of subsurface structures at the nanoscale. However, measurements in liquid environments remain complex, in particular in the subsurface domain. Here we introduce liquid-mode synthesizing atomic force microscopy (l-MSAFM) to study both the inner structures and the chemically induced intracellular impairments of living cells. Specifically, we visualize the intracellular stress effects of glyphosate on living keratinocytes skin cells. This new approach, l-MSAFM, for nanoscale imaging of living cell in their physiological environment or in presence of a chemical stress agent could resolve the loss of inner structures induced by glyphosate, the main component of a well-known pesticide (RoundUp™). This firsthand ability to monitor the cell's inner response to external stimuli non-destructively and in liquid, has the potential to unveil critical nanoscale mechanisms of life science.

Plasmon assisted thermal modulation in nanoparticles.

Single-particle interactions hold the promise of nanometer-scale devices in areas such as data communications and storage, nanolithography, waveguides, renewable energy and therapeutics. We propose that the collective electronic properties possessed by noble metal nanoparticles may be exploited for device actuation via the unapparent mechanism of plasmon-assisted heat generation and flux. The temperature dependence of the dielectric function and the thermal transport properties of the particles play the central role in the feasibility of the thermally-actuated system, however the behavior of these thermoplasmonic processes is unclear. We experimentally and computationally analyzed modulation via thermoplasmonic processes on a test system of gold (Au) nano-islands. Modulation and energy transport in discontinuous domains exhibited quantitatively different characteristics compared to thin films. The results have implications for all surface plasmon based nano-devices where inevitable small-scale thermal processes are present.

Critical issues in sensor science to aid food and water safety.

The stability of food and water supplies is widely recognized as a global issue of fundamental importance. Sensor development for food and water safety by nonconventional assays continues to overcome technological challenges. The delicate balance between attaining adequate limits of detection, chemical fingerprinting of the target species, dealing with the complex food matrix, and operating in difficult environments are still the focus of current efforts. While the traditional pursuit of robust recognition methods remains important, emerging engineered nanomaterials and nanotechnology promise better sensor performance but also bring about new challenges. Both advanced receptor-based sensors and emerging non-receptor-based physical sensors are evaluated for their critical challenges toward out-of-laboratory applications.

Spectroscopy and imaging of arrays of nanorods toward nanopolarimetry.

The polarization dependence of the optical scattering properties of two-dimensional arrays of metal nanostructures with sub-wavelength dimensions (nanoantennas) has been investigated. Arrays of 500 nm × 100 nm gold nanorods covering a 100 × 100 µm(2) area were fabricated with varying orientations on an electrically conductive substrate. The experimental and computational analysis of the angularly organized nanorods suggest potential use toward the development of an integrated polarimeter. Using the gold nanorods on a transparent substrate as a preliminary system, we show that in the proper spectral range the scattering properties of the structures may be tuned for such an application.

Nanometrology of delignified Populus using mode synthesizing atomic force microscopy.

The study of the spatially resolved physical and compositional properties of materials at the nanoscale is increasingly challenging due to the level of complexity of biological specimens such as those of interest in bioenergy production. Mode synthesizing atomic force microscopy (MSAFM) has emerged as a promising metrology tool for such studies. It is shown that, by tuning the mechanical excitation of the probe-sample system, MSAFM can be used to dynamically investigate the multifaceted complexity of plant cells. The results are argued to be of importance both for the characteristics of the invoked synthesized modes and for accessing new features of the samples. As a specific system to investigate, we present images of Populus, before and after a holopulping treatment, a crucial step in the biomass delignification process.

Discontinuity induced angular distribution of photon plasmon coupling.

Metal-dielectric transitions are important structures that can display a host of optical characteristics including excitation of plasmons. Metal-dielectric discontinuities can furthermore support plasmon excitation without a severe condition on the incident angle of the exciting photons. Using a semi-infinite thin gold film, we study surface plasmon (SP) excitation and the associated electromagnetic near-field distribution by recording the resulting plasmon interference patterns. In particular, we measure interference periods involving SPs at the scanable metal/air interface and the buried metal/glass one. Supported by optical near-field simulations and experiments, we demonstrate that the metal/glass surface plasmon is observable over a wide range of incident angles encompassing values above and below the critical incident angle. As a result, it is shown that scanning near-field microscopy can provide quantitative evaluation of the real part of the buried surface plasmon wavevector.

Optomechanical spectroscopy with broadband interferometric and quantum cascade laser sources.

The spectral tunability of semiconductor-metal multilayer structures can provide a channel for the conversion of light into useful mechanical actuation. Responses of suspended silicon, silicon nitride, chromium, gold, and aluminum microstructures are shown to be utilized as a detector for visible and IR spectroscopy. Both dispersive and interferometric approaches are investigated to delineate the potential use of the structures in spatially resolved spectroscopy and spectrally resolved microscopy. The thermoplasmonic, spectral absorption, interference effects, and the associated energy deposition that contributes to the mechanical response are discussed to describe the potential of optomechanical detection in future integrated spectrometers.

Virtual resonance and frequency difference generation by van der Waals interaction.

The ability to explore the interior of materials for the presence of inhomogeneities was recently demonstrated by mode synthesizing atomic force microscopy [L. Tetard, A. Passian, and T. Thundat, Nature Nanotech. 5, 105 (2009).]. Proposing a semiempirical nonlinear force, we show that difference frequency ω_ generation, regarded as the simplest synthesized mode, occurs optimally when the force is tuned to van der Waals form. From a parametric study of the probe-sample excitation, we show that the predicted ω_ oscillation agrees well with experiments. We then introduce the concept of virtual resonance to show that probe oscillations at ω_ can efficiently be enhanced.

Spectroscopy and atomic force microscopy of biomass.

Scanning probe microscopy has emerged as a powerful approach to a broader understanding of the molecular architecture of cell walls, which may shed light on the challenge of efficient cellulosic ethanol production. We have obtained preliminary images of both Populus and switchgrass samples using atomic force microscopy (AFM). The results show distinctive features that are shared by switchgrass and Populus. These features may be attributable to the lignocellulosic cell wall composition, as the collected images exhibit the characteristic macromolecular globule structures attributable to the lignocellulosic systems. Using both AFM and a single case of mode synthesizing atomic force microscopy (MSAFM) to characterize Populus, we obtained images that clearly show the cell wall structure. The results are of importance in providing a better understanding of the characteristic features of both mature cells as well as developing plant cells. In addition, we present spectroscopic investigation of the same samples.

Atomic force microscopy of silica nanoparticles and carbon nanohorns in macrophages and red blood cells.

The emerging interest in understanding the interactions of nanomaterial with biological systems necessitates imaging tools that capture the spatial and temporal distributions and attributes of the resulting nano-bio amalgam. Studies targeting organ specific response and/or nanoparticle-specific system toxicity would be profoundly benefited from tools that would allow imaging and tracking of in-vivo or in-vitro processes and particle-fate studies. Recently we demonstrated that mode synthesizing atomic force microscopy (MSAFM) can provide subsurface nanoscale information on the mechanical properties of materials at the nanoscale. However, the underlying mechanism of this imaging methodology is currently subject to theoretical and experimental investigation. In this paper we present further analysis by investigating tip-sample excitation forces associated with nanomechanical image formation. Images and force curves acquired under various operational frequencies and amplitudes are presented. We examine samples of mouse cells, where buried distributions of single-walled carbon nanohorns and silica nanoparticles are visualized.

New modes for subsurface atomic force microscopy through nanomechanical coupling.

Non-destructive, nanoscale characterization techniques are needed to understand both synthetic and biological materials. The atomic force microscope uses a force-sensing cantilever with a sharp tip to measure the topography and other properties of surfaces. As the tip is scanned over the surface it experiences attractive and repulsive forces that depend on the chemical and mechanical properties of the sample. Here we show that an atomic force microscope can obtain a range of surface and subsurface information by making use of the nonlinear nanomechanical coupling between the probe and the sample. This technique, which is called mode-synthesizing atomic force microscopy, relies on multi-harmonic forcing of the sample and the probe. A rich spectrum of first- and higher-order couplings is discovered, providing a multitude of new operational modes for force microscopy, and the capabilities of the technique are demonstrated by examining nanofabricated samples and plant cells.

Laser reflectometry of submegahertz liquid meniscus ringing.

Optical techniques that permit nondestructive probing of interfacial dynamics of various media are of key importance in numerous applications such as ellipsometry, mirage effect, and all-optical switching. Characterization of the various phases of microjet droplet formation yields important information for volume control, uniformity, velocity, and rate. The ringing of the meniscus and the associated relaxation time that occurs after droplet breakoff affect subsequent drop formation and is an indicator of the physical properties of the fluid. Using laser reflectometry, we present an analysis of the meniscus oscillations in an orifice of a piezoelectric microjet.

A spectroscopic investigation of the shape dependency of gold nanoparticles grown on roughened surfaces.

We present an investigation of the optical excitation of surface plasmons on Au films deposited on roughened surfaces by using a glancing angle deposition technique. By adjusting the deposition parameters of calcium fluoride and Au thin films, the spectral position of the surface plasmon resonances can be shifted through the green and into the near infrared region. In particular, we find that a rougher surface with obliquely deposited Au produces distinct spheroid-shaped nanoparticles (NPs). This results in stronger resonances with narrower linewidths, whereas smoother films result in broad red-shifted absorption. Imaging with an atomic force microscope and a scanning electron microscope provides information of NP geometry which are used as inputs for theoretical simulations of the observed spectra. The consequence of geometry distributions and inter-particle interactions are discussed. The ability to control the shape, therefore the optical response, of Au NPs over an arbitrarily large active area is of paramount importance in nano-science, especially in biological sensing applications and surface enhanced Raman scattering.

An experimental investigation of analog delay generation for dynamic control of microsensors and atomic force microscopy.

We present an implementation of pure-time-delay generation in analog signals located in the kilo-Hertz frequency band. The controlled constant delays that are produced engage in a feedback system to investigate the dynamic response of microcantilevers. Delayed systems offer a vast richness of eigenvalues resulting in the possibility of excitations at frequencies other than that of the fundamental mode. Different cantilever actuation and delay generation approaches are investigated and compared, and detailed experimental observation of the dynamic response of the system is presented. Based on our results, an acoustic excitation is devised that may be used as an efficient sensor.

Nonradiative surface plasmon assisted microscale Marangoni forces.

When a liquid droplet experiences a temperature inhomogeneity along its bounding surface, a surface energy gradient is engendered, which when, in a continuous sense, exceeding a threshold, results in a convective flow dissipating the energy. If the associated temperature gradients are sustained by the interface between the liquid and a supporting substrate, the induced flow can result in the lateral motion of the droplet overcoming the viscosity and inertia. Recently, pico-liter adsorbed and applied droplets were shown experimentally to be transported, and divided by the decay of optically excited surface plasmons into phonons in a thin gold foil. The decaying events locally modify the temperature of the liquid-solid interface, establishing microscale thermal gradients of sufficient magnitude for the droplet to undergo thermocapillary flow. We present experimental evidence of such gradients resulting in local surface modification associated with the excitation of surface plasmons. We show theoretically that the observed effect is due to Marangoni forces, and computationally visualize the flow characteristics for the experimental parameters. As an application based on our results, we propose a method for an all-optical modulation of light by light mediated by the droplet oscillations. Furthermore, the results have important consequences for microfluidics, droplet actuation, and simultaneous surface plasmon resonance sensing and spectroscopy.

Microscale Marangoni actuation: all-optical and all-electrical methods.

We present experimental results from an all-optical microfluidic platform that may be complimented by a thin film all-electrical network. Using these configurations we have studied the microfluidic convective flow systems of silicone oil, glycerol, and 1,3,5-trinitrotoluene on open surfaces through the production of surface tension gradients derived from thermal gradients. We show that sufficient localized thermal variation can be created utilizing surface plasmons and/or engaging individually addressable resistive thermal elements. Both studies manipulate fluids via Marangoni forces, each having their unique exploitable advantages. Surface plasmon excitation in metal foils are the driving engine of many physical-, chemical-, and bio-sensing applications. Incorporating, for the first time, the plasmon concept in microfluidics, our results thus demonstrate great potential for simultaneous fluid actuation and sensing.