Dynamics of secondary contamination from the interaction of high-power laser pulses with metal particles attached on the input surface of optical components.

We investigate the interaction of 355-nm and 1064-nm nanosecond laser pulses with nominally spherical metallic particles dispersed on the input surface of transparent substrates or high-reflectivity (HR) multilayer dielectric coatings, respectively. The objective is to elucidate the interaction mechanisms associated with contaminant-induced degradation and damage of transparent and reflective optical elements for high-power laser systems. The experiments involve time-resolved imaging capturing the dynamics of the interaction pathway, which includes plasma formation, particle ejection, and secondary contamination by droplets originating from the liquefied layer of the particle. The results suggest that HR coatings are more susceptible to secondary contamination by liquid droplets produced by the particles because of the different geometry of excitation and the location of plasma initiation. Modeling results focus on better understanding the melting of the particle surface, leading to ejections of liquid droplets and the pressure applied to the substrate, leading to mechanical damage.

Impact of laser-contaminant interaction on the performance of the protective capping layer of 1 ω high-reflection mirror coatings.

High dielectric constant multilayer coatings are commonly used on high-reflection mirrors for high-peak-power laser systems because of their high laser-damage resistance. However, surface contaminants often lead to damage upon laser exposure, thus limiting the mirror's lifetime and performance. One plausible approach to improve the overall mirror resistance against laser damage, including that induced by laser-contaminant coupling, is to coat the multilayers with a thin protective capping (absentee) layer on top of the multilayer coatings. An understanding of the underlying mechanism by which laser-particle interaction leads to capping layer damage is important for the rational design and selection of capping materials of high-reflection multilayer coatings. In this paper, we examine the responses of two candidate capping layer materials, made of SiO2 and Al2O3, over silica-hafnia multilayer coatings. These are exposed to a single oblique shot of a 1053 nm laser beam (fluence ∼10 J/cm2, pulse length 14 ns), in the presence of Ti particles on the surface. We find that the two capping layers show markedly different responses to the laser-particle interaction. The Al2O3 cap layer exhibits severe damage, with the capping layer becoming completely delaminated at the particle locations. The SiO2 capping layer, on the other hand, is only mildly modified by a shallow depression. Combining the observations with optical modeling and thermal/mechanical calculations, we argue that a high-temperature thermal field from plasma generated by the laser-particle interaction above a critical fluence is responsible for the surface modification of each capping layer. The great difference in damage behavior is mainly attributed to the large disparity in the thermal expansion coefficient of the two capping materials, with that of Al2O3 layer being about 15 times greater than that of SiO2.

How the overlapping timescales for peptide binding and terrace exposure lead to non-linear step dynamics during growth of calcium oxalate monohydrate.

Using in situ atomic force microscopy (AFM), we investigate the inhibition of calcium oxalate monohydrate (COM) step growth by aspartic acid-rich peptides and find that the magnitude of the effect depends on terrace lifetime. We then derive a time dependent step-pinning model in which average impurity spacing depends on the terrace lifetime as given by the ratio of step spacing to step speed. We show that the measured variation in step speed is well fit by the model and allows us to extract the characteristic peptide adsorption time. The model also predicts that a crossover in the timescales for impurity adsorption and terrace exposure leads to bistable growth dynamics described mathematically by a catastrophe. We observe this behavior experimentally both through the sudden drop in step speed to zero upon decrease of supersaturation as well as through fluctuations in step speed between the two limiting values at the point where the catastrophe occurs. We discuss the model's general applicability to macromolecular modifiers and biomineral phases.

Integration of atomic force microscopy and a microfluidic liquid cell for aqueous imaging and force spectroscopy.

We have designed and built a microfluidic liquid cell capable of high-resolution atomic force microscope (AFM) imaging and force spectroscopy. The liquid cell was assembled from three molded poly(dimethylsiloxane) (PDMS) pieces and integrated with commercially purchased probes. The AFM probe was embedded within the assembly such that the cantilever and tip protrude into the microfluidic channel. This channel is defined by the PDMS assembly on the top, a PDMS gasket on all four sides, and the sample substrate on the bottom, forming a liquid-tight seal. Our design features a low volume fluidic channel on the order of 50 nl, which is a reduction of over 3-5 orders of magnitude compared to several commercial liquid cells. This device facilitates testing at high shear rates and laminar flow conditions coupled with full AFM functionality in microfluidic aqueous environments, including execution of both force displacement curves and high resolution imaging.

Subnanometer atomic force microscopy of peptide-mineral interactions links clustering and competition to acceleration and catastrophe.

In vitro observations have revealed major effects on the structure, growth, and composition of biomineral phases, including stabilization of amorphous precursors, acceleration and inhibition of kinetics, and alteration of impurity signatures. However, deciphering the mechanistic sources of these effects has been problematic due to a lack of tools to resolve molecular structures on mineral surfaces during growth. Here we report atomic force microscopy investigations using a system designed to maximize resolution while minimizing contact force. By imaging the growth of calcium-oxalate monohydrate under the influence of aspartic-rich peptides at single-molecule resolution, we reveal how the unique interactions of polypeptides with mineral surfaces lead to acceleration, inhibition, and switching of growth between two distinct states. Interaction with the positively charged face of calcium-oxalate monohydrate leads to formation of a peptide film, but the slow adsorption kinetics and gradual relaxation to a well-bound state result in time-dependent effects. These include a positive feedback between peptide adsorption and step inhibition described by a mathematical catastrophe that results in growth hysteresis, characterized by rapid switching from fast to near-zero growth rates for very small reductions in supersaturation. Interactions with the negatively charged face result in formation of peptide clusters that impede step advancement. The result is a competition between accelerated solute attachment and inhibition due to blocking of the steps by the clusters. The findings have implications for control of pathological mineralization and suggest artificial strategies for directing crystallization.

Molecular modulation of calcium oxalate crystallization by osteopontin and citrate.

Calcium oxalate monohydrate (COM), which plays a functional role in plant physiology, is a source of chronic human disease, forming the major inorganic component of kidney stones. Understanding molecular mechanisms of biological control over COM crystallization is central to development of effective stone disease therapies and can help define general strategies for synthesizing biologically inspired materials. To date, research on COM modification by proteins and small molecules has not resolved the molecular-scale control mechanisms. Moreover, because proteins directing COM inhibition have been identified and sequenced, they provide a basis for general physiochemical investigations of biomineralization. Here, we report molecular-scale views of COM modulation by two urinary constituents, the protein osteopontin and citrate, a common therapeutic agent. Combining force microscopy with molecular modeling, we show that each controls growth habit and kinetics by pinning step motion on different faces through specific interactions in which both size and structure determine the effectiveness. Moreover, the results suggest potential for additive effects of simultaneous action by both modifiers to inhibit the overall growth of the crystal and demonstrate the utility of combining molecular imaging and modeling tools for understanding events underlying aberrant crystallization in disease.