Coupling buried etalon layers to an engraved metasurface for durable and large-aperture meta-optics.

Many optical applications that could potentially benefit from the design flexibility provided by the metasurface approach are being prohibited by the limited scalability of the fabrication and the robustness of the end-result structures when using a resonant meta-elements-based approach. An alternative demonstrated approach with superior scalability and robustness is substrate-engraved metasurfaces, based on medium mixing homogenization, yet it suffers from very limited optical response. Here we propose advancing this approach by coupling the metasurface with buried etalon layers, leading to enhancement in the optical response. A transfer matrix analysis is used to study the parameter space, predicting that the patterned reflectance values range of a beam shaper could be raised from only 4% to 30% when the metasurface is engraved in silica, and even up to 66% when engraved into higher-index oxides. Using the method proposed here, the phase difference range across the metasurface could be increased by 0.4 radians beyond the range achievable by a metasurface engraved in silica and could reach even higher values when embedded in higher-index materials. Full-wave numerical simulations are used to demonstrate a cylindrical metareflector and a metalens, further validating the analysis.

Quantized Grain Boundary States Promote Nanoparticle Alignment During Imperfect Oriented Attachment.

Oriented attachment (OA) has become a well-recognized mechanism for the growth of metal, ceramic, and biomineral crystals. While many computational and experimental studies of OA have shown that particles can attach with some misorientation then rotate to remove adjoining grain boundaries, the underlying atomistic pathways for this "imperfect OA" process remain the subject of debate. In this study, molecular dynamics and in situ transmission electron microscopy (TEM) are used to probe the crystallographic evolution of up to 30 gold nanoparticles during aggregation. It is found that Imperfect OA occurs because 1) grain boundaries become quantized when their size is comparable to the separation between constituent dislocations and 2) kinetic barriers associated with the glide of grain boundary dislocations are small. In support of these findings, TEM experiments show the formation of a single crystal aggregate after annealing nine initially misoriented, agglomerated particles with evidence of dislocation activity and twin formation during particle/grain alignment. These observations motivate future work on assembled nanocrystals with tailored defects and call for a revision of Read-Shockley models for grain boundary energies in nanocrystalline materials.

Scalable Light-Printing of Substrate-Engraved Free-Form Metasurfaces.

A key challenge for metasurface research is locally controlling at will the nanoscale geometric features on meter-scale apertures. Such a technology is expected to enable large aperture meta-optics and revolutionize fields such as long-range imaging, lasers, laser detection and ranging (LADAR), and optical communications. Furthermore, these applications are often more sensitive to light-induced and environmental degradation, which constrains the possible materials and fabrication process. Here, we present a relatively simple and scalable method to fabricate a substrate-engraved metasurface with locally printed index determined by induced illumination, which, therefore, addresses both the challenges of scalability and durability. In this process, a thin metal film is deposited onto a substrate and transformed into a mask via local laser-induced dewetting into nanoparticles. The substrate is then dry-etched through this mask, and selective mask removal finally reveals the metasurface. We show that masking by the local nanoparticle distribution, and, therefore, the local index, is dependent on the local light-induced dewetting temperature. We demonstrate printing of a free-form pattern engraved into a fused silica glass substrate using a laser raster scan. Large-scale spatially controlled engraving of metasurfaces has implications on other technological fields beyond optics, such as surface fluidics, acoustics, and thermomechanics.

Thermally ruggedized ITO transparent electrode films for high power optoelectronics.

We present two strategies to minimize laser damage in transparent conductive films. The first consists of improving heat dissipation by selection of substrates with high thermal diffusivity or by addition of capping layer heatsinks. The second is reduction of bulk energy absorption by lowering free carrier density and increasing mobility, while maintaining film conductance with thicker films. Multi-pulse laser damage tests were performed on tin-doped indium oxide (ITO) films configured to improve optical lifetime damage performance. Conditions where improvements were not observed are also described. When bulk heating is not the dominant damage process, discrete defect-induced damage limits damage behavior.

Efficient method for the measurement of lifetime optical damage performance of thin film coatings from laser damage size analysis.

A laser damage test method based on damage size analysis (DSA) is described that simplifies the derivation of the lifetime optical damage threshold of film materials critical in the design of devices used in high-repetition-rate, high-power laser systems. The DSA method presented here is solely based on imaging to measure the damage site size produced from exposure to a known Gaussian-shaped beam with a fixed, systematically selected fluence well above the ablation threshold. The method locates the damage boundary produced from repeated exposures, using images with a high contrast, and maps it to the beam profile to extract a lifetime laser damage fluence threshold value. We validate the DSA approach using a few relevant transparent film material systems and by comparing it to the standard S/1 laser damage test method. The DSA method can be more efficient and accelerate materials development and validation necessary to support the design of high-power repetition-rated lasers and optoelectronic devices.

Laser damage mechanisms in conductive widegap semiconductor films.

Laser damage mechanisms of two conductive wide-bandgap semiconductor films - indium tin oxide (ITO) and silicon doped GaN (Si:GaN) were studied via microscopy, spectroscopy, photoluminescence (PL), and elemental analysis. Nanosecond laser pulse exposures with a laser photon energy (1.03 eV, 1064 nm) smaller than the conductive films bandgaps were applied and radically different film damage morphologies were produced. The laser damaged ITO film exhibited deterministic features of thermal degradation. In contrast, laser damage in the Si:GaN film resulted in highly localized eruptions originating at interfaces. For ITO, thermally driven damage was related to free carrier absorption and, for GaN, carbon complexes were proposed as potential damage precursors or markers.

Damage on fused silica optics caused by laser ablation of surface-bound microparticles.

High peak power laser systems are vulnerable to performance degradation due to particulate contamination on optical surfaces. In this work, we show using model contaminant particles that their optical properties decisively determine the nature of the optical damage. Borosilicate particles with low intrinsic optical absorption undergo ablation initiating in their sub-surface, leading to brittle fragmentation, distributed plasma formation, material dispersal and ultimately can lead to micro-fractures in the substrate optical surface. In contrast, energy coupling into metallic particles is highly localized near the particle-substrate interface leading to the formation of a confined plasma and subsequent etching of the substrate surface, accompanied by particle ejection driven by the recoil momentum of the ablation plume. While the tendency to create fractured surface pitting from borosilicate is stochastic, the smooth ablation pits created by metal particles is deterministic, with pit depths scaling linearly with laser fluence. A simple model is employed which predicts ~3x electric field intensity enhancement from surface-bound fragments. In addition, our results suggest that the amount of energy deposited in metal particles is at least twice that in transparent particles.

Facile fabrication of a superhydrophobic cage by laser direct writing for site-specific colloidal self-assembled photonic crystal.

Micron-sized ablated surface structures with nano-sized 'bumpy' structures were produced by femtosecond (fs) laser ablation of polytetrafluoroethylene (PTFE) film under ambient conditions. Upon just a single step, the processed surface exhibited hierarchical micro/nano morphology. In addition, due to the tribological properties of PTFE, polydimethylsiloxane (PDMS) could be replicated from the laser-ablated PTFE surface without anti-adhesive surface treatment. By controlling the design of the ablated patterns, tunable wettability and superhydrophobicity were achieved on both PTFE and PDMS replica surfaces. Furthermore, using fs laser ablation direct writing, a flexible superhydrophobic PDMS cage formed by superhydrophobic patterns encompassing the unmodified region was demonstrated for aqueous droplet positioning and trapping. Through evaporation-driven colloidal self-assembly in this superhydrophobic cage, a colloidal droplet containing polystyrene (PS) particles dried into a self-assembled photonic crystal, whose optical band gap could be manipulated by the particle size.

Light scattering from laser induced pit ensembles on high power laser optics.

Far-field light scattering characteristics from randomly arranged shallow Gaussian-like shaped laser induced pits, found on optics exposed to high energy laser pulses, is studied. Closed-form expressions for the far-field intensity distribution and scattered power are derived for individual pits and validated using numerical calculations of both Fourier optics and FDTD solutions to Maxwell's equations. It is found that the scattered power is proportional to the square of the pit width and approximately also to the square of the pit depth, with the proportionality factor scaling with pit depth. As a result, the power scattered from shallow pitted optics is expected to be substantially lower than assuming complete scattering from the total visible footprint of the pits.

Directed dewetting of amorphous silicon film by a donut-shaped laser pulse.

Irradiation of a thin film with a beam-shaped laser is proposed to achieve site-selectively controlled dewetting of the film into nanoscale structures. As a proof of concept, the laser-directed dewetting of an amorphous silicon thin film on a glass substrate is demonstrated using a donut-shaped laser beam. Upon irradiation of a single laser pulse, the silicon film melts and dewets on the substrate surface. The irradiation with the donut beam induces an unconventional lateral temperature profile in the film, leading to thermocapillary-induced transport of the molten silicon to the center of the beam spot. Upon solidification, the ultrathin amorphous silicon film is transformed to a crystalline silicon nanodome of increased height. This morphological change enables further dimensional reduction of the nanodome as well as removal of the surrounding film material by isotropic silicon etching. These results suggest that laser-based dewetting of thin films can be an effective way for scalable manufacturing of patterned nanostructures.

Nanoscale surface tracking of laser material processing using phase shifting diffraction interferometry.

Phase shifting diffraction interferometry (PSDI) was adapted to provide real-time feedback control of a laser-based chemical vapor deposition (LCVD) process with nanometer scale sensitivity. PSDI measurements of laser heated BK7 and fused silica substrates were used to validate a finite element model that accounts for both refractive index changes and displacement contributions to the material response. Utilizing PSDI and accounting for the kinetics of the modeled thermomechanical response, increased control of the LCVD process was obtained. This approach to surface tracking is useful in applications where extreme environments on the working surface require back-side optical probing through the substrate.

Characterization of ejected fused silica particles following surface breakdown with nanosecond pulses.

The light emission produced near the surface of fused silica following laser-induced breakdown on the exit surface was spatially and spectrally resolved. This signal is in part generated by ejected particles while traveling outside the hot ionized region. The thermal emission produced by the particles can be separated from the plasma emission near the surface and its spectral characteristics provide information on the temperature of the particles after ejection from the surface. Assuming the emission is thermal in origin, data suggest an initial average temperature on the order of at least 0.5 eV.

Evaporation kinetics of laser heated silica in reactive and inert gases based on near-equilibrium dynamics.

Evaporation kinetics of fused silica were measured up to ≈3000K using CO(2) laser heating, while solid-gas phase chemistry of silica was assessed with hydrogen, air, and nitrogen. Enhanced evaporation in hydrogen was attributed to an additional reduction pathway, while oxidizing conditions pushed the reaction backwards. The observed mass transport limitations supported use of a near-equilibrium analysis for interpreting kinetic data. A semi-empirical model of the evaporation kinetics is derived that accounts for heating, gas chemistry and transport properties. The approach described should have application to materials laser processing, and in applications requiring knowledge of thermal decomposition chemistry under extreme temperatures.

Subnanometer replica molding of molecular steps on ionic crystals.

Replica molding with elastomeric polymers has been used routinely to replicate features less than 10 nm in size. Because the theoretical limit of this technique is set by polymer-surface interactions, atomic radii, and accessible volumes, replication at subnanometer length scales should be possible. Using polydimethylsiloxane to create a mold and polyurethane to form the replica, we demonstrate replication of elementary steps 3-5 Å in height that define the minimum separation between molecular layers in the lattices of the ionic crystals potassium dihydrogen phosphate and calcite. This work establishes the operation of replica molding at the molecular scale.

Scanning probe-based fabrication of 3D nanostructures via affinity templates, functional RNA, and meniscus-mediated surface remodeling.

Developing generic platforms to organize discrete molecular elements and nanostructures into deterministic patterns on surfaces is one of the central challenges in the field of nanotechnology. Here we review three applications of the atomic force microscope (AFM) that address this challenge. In the first, we use two-step nanografting to create patterns of self-assembled monolayers (SAMs) to drive the organization of virus particles that have been either genetically or chemically modified to bind to the SAMs. Virus-SAM chemistries are described that provide irreversible and reversible binding, respectively. In the second, we use similar SAM patterns as affinity templates that have been designed to covalently bind oligonucleotides engineered to bind to the SAMs and selected for their ability to mediate the subsequent growth of metallic nanocrystals. In the final application, the liquid meniscus that condenses at the AFM tip-substrate contact is used as a physical tool to both modulate the surface topography of a water soluble substrate and guide the hierarchical assembly of Au nanoparticles into nanowires. All three approaches can be generalized to meet the requirements of a wide variety of materials systems and thereby provide a potential route toward development of a generic platform for molecular and materials organization.

Solvent-mediated repair and patterning of surfaces by AFM.

A tip-based approach to shaping surfaces of soluble materials with nanometer-scale control is reported. The proposed method can be used, for example, to eliminate defects and inhomogeneities in surface shape, repair mechanical or laser induced damage to surfaces, or perform 3D lithography on the length scale of an AFM tip. The phenomenon that enables smoothing and repair of surfaces is based on the transport of material from regions of high to low curvature within the solution meniscus formed in a solvent-containing atmosphere between the surface in question and an AFM tip scanned over the surface. Using in situ AFM measurements of the kinetics of surface remodeling on KDP (KH(2)PO(4)) crystals in humid air, we show that redistribution of solute material during relaxation of grooves and mounds is driven by a reduction in surface free energy as described by the Gibbs-Thomson law. We find that the perturbation from a flat interface evolves according to the diffusion equation, where the effective diffusivity is determined by the product of the surface stiffness and the step kinetic coefficient. We also show that, surprisingly, if the tip is instead scanned over or kept stationary above an atomically flat area of the surface, a convex structure is formed, with a diameter that is controlled by the dimensions of the meniscus, indicating that the presence of the tip and meniscus reduces the substrate chemical potential beneath that of the free surface. This allows one to create nanometer-scale 3D structures of arbitrary shape without the removal of substrate material or the use of extrinsic masks or chemical compounds. Potential applications of these tip-based phenomena are discussed.

Implementation of an optical method for the real-time determination of uniaxial strain and vessel mechanics.

The determination of the mechanical properties of vascular growth substrates has seen increasing interest in the bioengineering field. Mechanical features such as rupture strength, compliance characteristics, and viscoelastic properties of vascular grafts are important for their design and are indicative of their success in vivo. Thus a simple inexpensive measurement technique for these parameters would be useful. In this report we describe the implementation of an optical method for the measurement of vessel distention under a transluminal pressure gradient. It is based on the concept of laser light occlusion and allows for real time noncontact diameter measurements of hollow vessels < or = 2 cm. We demonstrate precise and reproducible measurements of diameter changes of less than 10 microm and, further, with the simultaneous determination of both strain and luminal pressure, were able to determine the elastic modulus of commercially available polymeric vessels. Comparison of the manufacturer specifications and our own measurement of the elastic modulus of these vessels, validate the effectiveness of our system. The advantages of this technique are its relative low cost, ease of implementation, high resolution, and flexibility stemming from its modular setup.

Optical properties of an immobilized DNA monolayer from 255 to 700 nm.

The real (n) and imaginary (k) refractive indices of an immobilized monolayer of 27 nucleotide (nt) single stranded DNA (ssDNA) and the corresponding double stranded DNA (dsDNA) are measured in the 255-700 nm range. Multiple techniques are used to obtain consistent estimation. The coverage is approximately 6.5% with an average interchain distance of tethered ssDNA molecules of approximately 11.8 nm, which is significantly larger than the "footprint" of the chain on the surface. The measured increase in n by approximately 5% between the ssDNA and the dsDNA is 20% smaller than the expected change due to doubling of the molecular weight. The change in k is not significant, indicating that the electron delocalization effect expected in dsDNA due to base pair stacking is not important at optical frequencies.

Chronic pulsatile shear stress alters insulin-like growth factor-I (IGF-I) binding protein release in vitro.

Insulin-like growth factor-I (IGF-I) is a potent smooth muscle cell mitogen indicated to have a role in vascular disease. IGF-I stimulates proliferation via receptor activation but its activity is mediated by IGF binding proteins (IGFBPs). Since hemodynamics have been linked to vascular proliferative disorders, we studied how pulsatile low (5 +/- 2 dynes/cm2) and high (23 +/- 8 dynes/cm2) shear stresses impacted IGFBP metabolism in bovine aortic endothelial cells using the Cellmax capillary system. We modeled the pulsatile flow in our system using the Womersley model for flow inside a rigid tube and harmonic analysis revealed that the flow was sinusoidal with a frequency of approximately 0.3 Hz for both shear stress treatments. Laminar flow was confirmed and the phase lag between the pressure and the flow found to be insignificant. Thus, our study provides a necessary characterization of this in vitro system as well as an investigation into how shear impacts the IGF axis. We found a significant difference in IGFBP distribution between treatments and, given that IGFBPs regulate IGF-I activity and that IGF-I-independent activities have been suggested for IGFBP-3, suggest that shear stress may indirectly regulate IGF-I activity, and, by extension, the effect of IGF-I on vascular pathologies.

Chronic pulsatile shear stress impacts synthesis of proteoglycans by endothelial cells: effect on platelet aggregation and coagulation.

Endothelial-derived proteoglycans are important regulators of the coagulation-pathway in vivo and our primary objective of this study was to determine whether chronic shear stress affected the synthesis, release, and activity of proteoglycans from bovine aortic endothelial cells (BAEC). BAEC were cultured under shear and proteoglycans were purified from BAEC conditioned media and analyzed using both anionic exchange and size exclusion chromatography. The overall amount of proteoglycans produced per cell was significantly greater for the high shear-treated samples compared to the low shear-treated samples indicating that the shear magnitude did impact cell responsiveness. While overall size and composition of the proteoglycans and glycosaminoglycan (GAG) side chains were not altered by shear, the relative proportion of the high and low molecular weight species was inversely related to shear and differed significantly from that found under static tissue culture conditions. Moreover, a unique proteoglycan peak was identified from low shear stress (5 +/- 2 dynes/cm(2)) conditioned media when compared to high shear conditions (23 +/- 8 dynes/cm(2)) via anionic exchange chromatography, suggesting that subtle changes in the GAG structures may impact activity of these molecules. In order to characterize whether these changes impacted proteoglycan function, we studied the effects of shear specific proteoglycans on the inhibition of thrombin-induced human platelet aggregation as well as on platelet-fibrin clot dynamics. Proteoglycans from high shear-treated samples were less effective inhibitors of both platelet aggregation and blood coagulation inhibition than proteoglycans from low shear-treated samples and both were less effective than proteoglycans isolated from static tissue culture samples. However, due to changes in the overall proteoglycan synthesis and release rate, the high and low shear-treated sample had essentially identical effects on these activities, suggesting that the cells were able to compensate for stress-induced proteoglycan changes. Our data suggests that shear stress, by altering proteoglycan synthesis and fine structure, may play a role in maintaining vascular hemodynamics and hemostasis.