A novel, to the best of our knowledge, method of wet chemical etching of sapphire workpieces (such as optics, wafers, windows, and cones), called the sapphire advanced mitigation process (or sapphire AMP), has been developed that exposes sub-surface mechanical damage created during the optical fabrication process and significantly enhances the surface laser damage resistance ($ \gt {2{\times}}$>2×) and mechanical strength (up to $\sim{2.6{\times}}$∼2.6×). Sapphire AMP involves first treating the workpiece with a mixture of sulfuric and phosphoric acid $([{\rm H_{2}{\rm SO_{4}}}]:[{\rm H_{3}{\rm PO_{4}}}]=1:3)$([H2SO4]:[H3PO4]=1:3) at 220°C, followed with phosphoric acid at 160°C, then with sodium hydroxide base (NaOH) and surfactant at 40°C, and finally with a high-pressure deionized water spray rinse. Sapphire AMP has been demonstrated on both A- and C-plane sapphire workpieces. The mechanism of this etch process involves the reaction of the sapphire $({\rm Al_{2}}{\rm O_{3}})$(Al2O3) surface with sulfuric acid $({\rm H_{2}}{\rm SO_{4}})$(H2SO4) forming aluminum sulfate $[{{\rm Al}_2}{({{\rm SO}_4})_3}]$[Al2(SO4)3], which has low solubility. The high phosphoric acid content in the first and second steps of sapphire AMP results in the efficient conversion of ${{\rm Al}_2}{({{\rm SO}_4})_3}$Al2(SO4)3 to aluminum phosphate $({\rm AlPO_{4}})$(AlPO4), which is very soluble, greatly reducing reaction product redeposition on the workpiece surface. Sapphire AMP is shown to expose sub-surface mechanical damage on the sapphire surface created during the grinding and polishing processes, whose etched morphology has either isotropic or anisotropic evolution depending on the nature of the initial surface damage. Sapphire AMP was also designed to remove the key known surface, laser absorbing precursors (namely, foreign chemical impurities, the fracture surface layer of preexisting sub-surface damage, and reaction product or foreign species redeposition or precipitation). Static and sliding indention induced surface microfractures on sapphire are shown after sapphire AMP to have a significant decrease in the fast photoluminescence intensity (a known metric for measuring the degree of laser damaging absorbing precursors). In addition, the onset of laser damage (at 351 nm 3 ns) on sapphire AMP treated workpieces was shown to increase in fluence from $\sim{4}$∼4 to $ \gt {9}.{5}\;{{\rm J/cm}^2}$>9.5J/cm2. Finally, biaxial ball-on-ring mechanical tests on sapphire disks showed an increase in the failure stress from 340 MPa (with pre-existing 28 µm flaws) to $\sim{900}\;{\rm MPa}$∼900MPa after sapphire AMP, which is attributed to the blunting of the surface microfractures.

A series of static and sliding indentation (ie, scratching) was performed and characterized on a wide range of optical workpiece materials [single crystals of Al2O3 (sapphire), SiC, Y3Al5O12 (YAG), CaF2, and LiB3O5 (LBO); a SiO2-Al2O3-P2O5-Li2O glass ceramic (Zerodur); and glasses of SiO2:TiO2 (ULE), SiO2 (fused silica), and P2O5-Al2O3-K2O-BaO (Phosphate)] at various applied loads using various indenters (Vickers, 10 mu m conical, and 200 mu m conical). Despite having different load dependencies, the lateral crack depth formed during sliding indentation quantitatively scales with that formed during static indentation, explaining why static indentation has been historically effective in describing various grinding parameters. Depending on the indenter geometry, the amount of residual trench damage (plastic deformation and local fracturing) during sliding indentation was often enhanced by more than an order of magnitude compared with static indentation. A simple ploughing scratch model, which considers both tangential and normal stresses (where the tangential stress is amplified by relatively small tangential contact area), explains this enhancement and other observed trends. Accounting for the high correlation between residual trench depth and volumetric fracturing, the model is extended to estimate the amount of fracture damage as a function of the material properties of the workpiece, indenter geometry, and applied load. Such a model has utility in the design of optimized grinding processes, particularly the abrasive geometry. Finally, at higher loads (>1 N), lateral cracks were often observed to preferentially propagate in the forward scratching direction, as opposed to perpendicular to the scratch as typically observed. High-speed imaging of the scratch process confirms that these cracks propagate ahead of the sliding indenter during the scratching event. Finite element stress analysis suggests the ploughing frictional forces increase the mode I tensile stresses at the leading edge of the sliding indenter explaining the direction of crack propagation of such cracks.

The nanomechanical deformations on a broad range of optical material surfaces (single crystals of Al2O3 [sapphire], SiC, Y3Al5O12 [YAG], CaF2, and LiB3O5 [LBO]; a SiO2-Al2O3-P2O5-Li2O glass-ceramics [Zerodur]; and glasses of SiO2:TiO2 [ULE], SiO2 [fused silica], and P2O5-Al2O3-K2O-BaO [Phosphate]) near the elastic-plastic load boundary have been measured by nanoindentation and nanoscratching to mimic the nanoplastic removal caused by a single slurry particle during polishing. Nanoindenation in air was performed to determine the workpiece hardness at various loads using a commercial nanoindenter with a Berkovich tip. Similarly, an atomic force microscope (AFM) with a stiff diamond coated tip (150nm radius) was used to produce nanoplastic scratches in air and aqueous environments over a range of applied loads (20-170N). The resulting nanoplastic deformation of the nanoscratches were used to calculate the removal function (i.e., depth per pass) which ranged from 0.18 to 3.6nm per pass for these materials. A linear correlation between the nanoplastic removal function and the polishing rate (using a fixed polishing process with colloidal silica slurry on a polyurethane pad) of these materials was observed implying that: (a) the polishing mechanism using colloidal silica slurry can be dominated by mechanical rather than chemical interactions; and (b) the nanoplastic removal function, as opposed to interface particle interactions, is the controlling factor for the polishing material removal rate. Furthermore, this correlation is consistent with the Ensemble Hertzian Multi-Gap (EHMG) microscopic material removal rate model described previously. The nanoplastic removal depth was also found to correlate to the measured nanoindentation hardness (H-1) of the optical material, scaling as H-1(-3.5). Two-dimensional (2D) finite element analysis simulations of nanoindentation showed a similar nonlinear dependence of plastic deformation with the workpiece material hardness. The findings of this study are used to determine an effective Preston coefficient for the material removal rate expression and enhance the predictive nature of the nanoplastic polishing rate for various materials utilizing their material properties.

A series of controlled grinding experiments, utilizing loose or fixed abrasives of either alumina or diamond at various particle sizes, were performed on a wide range of optical workpiece materials [single crystals of Al2O3 (sapphire), SiC, Y3Al5O12 (YAG), CaF2, and LiB3O5 (LBO); a SiO2-Al2O3-P2O5-Li2O glass ceramic (Zerodur); and glasses of SiO2:TiO2 (ULE), SiO2 (fused silica), and P2O5-Al2O3-K2O-BaO (phosphate)]. The material removal rate, surface roughness, and morphology of surface fractures were measured. Separately, Vickers indentation was performed on the workpieces, and the depths of various crack types as a function of applied load was measured. Single pass grinding experiments showed distinct differences in the spatial pattern of surface fracturing between the loose alumina abrasive (isolated indent-type lateral cracking) and the loose or fixed diamond abrasive (scratch-type elongated lateral cracking). Each of the grinding methods had a removal rate and roughness that scaled with the lateral crack slope, sℓ (i.e., the rate of increase in lateral crack depth with the applied load) of the workpiece material. A grinding model (based on the volumetric removal of lateral cracks accounting for neighboring lateral crack removal efficiency and the fraction of abrasive particles leading to fracture initiation) and a roughness model (based on the depth of lateral cracks or the interface gap between the workpiece and lap) are shown to quantitatively describe the material removal rate and roughness as a function of workpiece material, abrasive size, applied pressure, and relative velocity. This broad, multiprocess variable grinding model can serve as a predictive tool for estimating grinding rates and surface roughness for various grinding processes on different workpiece materials.

The following study presents useful quantitative rules, based on fundamental mechanisms, for the determining the grinding & polishing rate and grinding roughness during optical fabrication for a variety of optical workpiece materials.

A partial charge-based chemical polishing model has been developed, which can serve as metric for describing the relative polishing material removal rate for different combinations of slurries and workpieces. A series of controlled polishing experiments utilizing a variety of colloidal polishing slurries (SiO2, CeO2, ZrO2, MgO, Sb2O5) and optical materials [single crystals of Al2O3 (sapphire), SiC, Y3Al5O12 (YAG), CaF2, and LiB3O5 (LBO); a SiO2-Al2O3-P2O5-Li2O glass ceramic (Zerodur); and glasses of SiO2:TiO2 (ULE), SiO2 (fused silica), and P2O5-Al2O3-K2O-BaO (Phosphate)] was performed and its material removal rate was measured. As previously proposed by Cook (J Non-Cryst Solids. 1990;120:152), for many polishing systems, the removal rate is governed by a series of chemical reactions which include the formation of a surface hydroxide, followed by condensation of that hydroxyl moiety with the polishing particle, and a subsequent hydrolysis reaction. The rate of condensation can often be the rate limiting step, thus it can determine the polishing material removal rate. By largely keeping the numerous other factors that influence material removal rate fixed (such as due to particle size distributions, interface interactions, pad topography, kinematics, and applied pressure), the material removal rate is shown to scale exponentially with the partial charge difference ((wp-s)) between the workpiece and polishing slurry particle for many of the slurry-workpiece combinations indicating that condensation rate is the rate limiting step. The partial charge () describes the equilibrium distribution of electron density between chemically bonded atoms and is related to the electronegativity of the atoms chemically bonded to one another. This partial charge model also explains the age-old experimental finding of why cerium oxide is the most effective polishing slurry for chemical removal of many workpieces. Some of the slurry-workpiece combinations that did not follow the partial charge dependence offer insight to other removal mechanisms or rate limiting reaction pathways.

Particle adsorption was explored in a model optical polishing system, consisting of silica colloids and like-charged silica surfaces. The adsorption was monitored in situ under various suspension conditions, in the absence of surfactants or organic modifiers, using a quartz crystal microbalance with dissipation monitoring (QCM-D). Changes in surface coverage with particle concentration, particle size, pH, ionic strength and ionic composition were quantified by QCM-D and further characterized ex situ by atomic force microscopy (AFM). A Monte Carlo model was used to describe the kinetics of particle deposition and provide insights on scaling with particle concentration. Transitions from near-zero adsorption to measurable adsorption were compared with equilibrium predictions made using the Deraguin-Verwey-Landau-Overbeek (DLVO) theory. In addition, the impact of silica surface roughness on the propensity for particle adsorption was studied on various spatial scale lengths by intentionally roughening the QCM sensor surface using polishing methods. It was found that a change in silica surface roughness at the AFM scale from 1.3 nm root-mean-square (rms) to 2.7 nm rms resulted in an increase in silica particle adsorption of 3-fold for 50-nm diameter particles and 1.3-fold for 100-nm diameter particles far exceeding adsorption observed by altering suspension conditions alone, potentially because roughness at the proper scale reduces the total separation distance between particle and surface. (C) 2017 Elsevier B.V. All rights reserved.

During optical glass polishing, a number of interactions between the workpiece (i.e., glass), polishing slurry, and pad can influence the resulting workpiece roughness at different spatial scale lengths. In our previous studies, the particle size distribution of the slurry, the pad topography, and the amount of material removed by a single particle on the workpiece were shown to strongly correlate with roughness at AFM scale lengths (nm-m) and weakly at -roughness scale lengths (m-mm). In this study, the polishing slurry pH and the generation of glass removal products are shown to influence the slurry particle spatial and height distribution at the polishing interface and the resulting -roughness of the glass workpiece. A series of fused silica and phosphate glass samples were polished with various ceria and colloidal silica slurries over a range of slurry pH, and the resulting AFM roughness and -roughness were measured. The AFM roughness was largely invariant with pH, suggesting that the removal function of a single particle is unchanged with pH. However, the -roughness changed significantly, increasing linearly with pH for phosphate glass and having a maximum at an intermediate pH for fused silica. In addition, the spatial and height distribution of slurry particles on the pad (as measured by laser confocal microscopy) was determined to be distinctly different at low and high pH during phosphate glass polishing. Also, the zeta potential as a function of pH was measured for the workpiece, slurry, and pad with and without surrogate glass products (K3PO4 for phosphate glass and Si(OH)(4) for silica) to assess the role of interfacial charge during polishing. The addition of K3PO4 significantly raised the zeta potential, whereas addition of Si(OH)(4) had little effect on the zeta potential. An electrostatic DLVO three-body force model, using the measured zeta potentials, was used to calculate the particle-particle, particle-workpiece, and particle-pad attractive and repulsive forces as a function of pH and the incorporation of glass products at the interface. The model predicted an increase in particle-pad attraction with an increase in pH and phosphate glass products consistent with the measured slurry distribution on the pads during phosphate glass polishing. Finally, a slurry island distribution gap (IDG) model has been formulated which utilizes the measured interface slurry distributions and a load balance to determine the interface gap, the contact area fraction, and the load on each slurry island. The IDG model was then used to simulate the workpiece surface topography and -roughness; the results show an increase in roughness with pH similar to that observed experimentally.

Development of optical elements that enable tailored modification of the refractive index during exposure to high-power laser pulses provides opportunity to control laser coherence and focal-spot characteristics. Our approach is based on activation of induced and/or spontaneously generated defect centers in large-bandgap materials.

The nanomechanical deformations on glass surfaces near the elastic–plastic load boundary have been measured on various glasses by nanoscratching using an atomic force microscope ( AFM ) to mimic the mechanical interactions of polishing particles during optical polishing. Nanoscratches were created in air and aqueous environments using a 150‐nm radius diamond‐coated tip on polished fused silica, borosilicate, and phosphate glass surfaces; the topology of the nanoscratches were then characterized by AFM . Using load ranges expected on slurry particles during glass polishing (0.05–200 μN), plastic‐type scratches were observed with depths in the nm range. Nanoscratching in air generally showed deeper & narrower scratches with more pileup compared to nanoscratching in water, especially on fused silica glass. The critical load needed to observe plastic deformation was determined to range from 0.2–1.2 μN for the three glasses. For phosphate glass, the load dependence of the removal depth was consistent with that expected from Hertzian mechanics. However, for fused silica and borosilicate glass in this load range, the deformation depth showed a weak dependence with load. Using a sub‐ T g annealing technique, material relaxation was observed on the nanoscratches, suggesting that a significant fraction of the deformation was due to densification on fused silica and borosilicate glass. Repeated nanoscratching at the same location was utilized for determining the effective incremental plastic removal depth. The incremental removal depth decreased with increase in number of passes, stabilizing after ~10 passes. In water, the removal depths were determined as 0.3–0.55 nm/pass for fused silica, 0.85 nm/pass for borosilicate glass, and 2.4 nm/pass for phosphate glass. The combined nanoscratching results were utilized to define the composite removal function (i.e., removal depth) for a single polishing particle as a function of load, spanning the chemical to the plastic removal regimes. This removal function serves as an important set of parameters in understanding material removal during polishing and the resulting workpiece surface roughness.

Glass optics with ultra‐low roughness surfaces (<2 Å rms) are strongly desired for high‐end optical applications (e.g., lasers, spectroscopy, etc.). The complex microscopic interactions that occur between slurry particles and the glass workpiece during optical polishing ultimately determine the removal rate and resulting surface roughness of the workpiece. In this study, a comprehensive set of 100 mm diameter glass samples (fused silica, phosphate, and borosilicate) were polished using various slurry particle size distributions (PSD), slurry concentrations, and pad treatments. The removal rate and surface roughness of the glasses were characterized using white light interferometry and atomic force microscopy. The material removal mechanism for a given slurry particle is proposed to occur via nano‐plastic deformation (plastic removal) or via chemical reaction (molecular removal) depending on the slurry particle load on the glass surface. Using an expanded Hertzian contact model, called the Ensemble Hertzian Multi‐gap (EHMG) model, a platform has been developed to understand the microscopic interface interactions and to predict trends of the removal rate and surface roughness for a variety of polishing parameters. The EHMG model is based on multiple Hertzian contacts of slurry particles at the workpiece–pad interface in which the pad deflection and the effective interface gap at each pad asperity height are determined. Using this, the interface contact area and each particle's penetration, load, and contact zone are determined which are used to calculate the material removal rate and simulate the surface roughness. Each of the key polishing variables investigated is shown to affect the material removal rate, whose changes are dominated by very different microscopic interactions. Slurry PSD impacts the load per particle distribution and the fraction of particles removing material by plastic removal. The slurry concentration impacts the areal number density of particles and fraction of load on particles versus pad. The pad topography impacts the fraction of pad area making contact with the workpiece. The glass composition predominantly impacts the depth of plastic removal. Also, the results show that the dominant factor controlling surface roughness is the slurry PSD followed by the glass material's removal function and the pad topography. The model compares well with the experimental data over a variety of polishing conditions for both removal rate and roughness and can be extended to provide insights and strategies to develop practical, economic processes for obtaining ultra‐low roughness surfaces while simultaneously maintaining high material removal rates.

Intense laser pulses can cause superheating of the near-surface volume of materials. This mechanism is widely used in applications such as laser micromachining, laser ablation, or laser assisted thin film deposition. The relaxation of the near solid density superheated material is not well understood, however. In this work, we investigate the relaxation dynamics of the superheated material formed in several dielectrics with widely differing physical properties. The results suggest that the relaxation process involves a number of distinct phases, which include the delayed explosive ejection of microscale particles starting after the pressure of the superheated material is reduced to about 4 GPa and for a time duration on the order of 1 mu s. The appearance of a subset of collected ejected particles in fused silica is similar to that of micro-tektites and provides information about the state of the superheated material at the time of ejection. These results advance our understanding of a key aspect of the laser-material interaction pathway and can lead to optimization of associated applications ranging from material processing to laser surgery.

The chemical characteristics and the proposed formation mechanisms of the modified surface layer (called the Beilby layer) on polished fused silica glasses are described. Fused silica glass samples were polished using different slurries, polyurethane pads, and at different rotation rates. The concentration profiles of several key contaminants, such as Ce, K, and H, were measured in the near surface layer of the polished samples using Secondary Ion Mass Spectroscopy (SIMS). The penetration of K, originating from KOH used for pH control during polishing, decreased with increase in polishing material removal rate. In contrast, penetration of the Ce and H increased with increase in polishing removal rate. In addition, Ce penetration was largely independent of the other polishing parameters (e.g., particle size distribution and the properties of the polishing pad). The resulting K concentration depth profiles are described using a two‐step diffusion process: (1) steady‐state moving boundary diffusion (due to material removal during polishing) followed by (2) simple diffusion during ambient postpolishing storage. Using known alkali metal diffusion coefficients in fused silica glass, this diffusion model predicts concentration profiles that are consistent with the measured data at various polishing material removal rates. On the other hand, the observed Ce profiles are inconsistent with diffusion based transport. Rather we propose that Ce penetration is governed by the ratio of Ce–O–Si and Si–O–Si hydrolysis rates; where this ratio increases with interface temperature (which increases with polishing material removal rate) resulting in greater Ce penetration into the Beilby layer. Calculated Ce surface concentrations using this mechanism are in good agreement to the observed change in measured Ce surface concentrations with polishing material removal rate. These new insights into the chemistry of the Beilby layer, combined together with details of the single particle removal function during polishing, are used to develop a more detailed and quantitative picture of the polishing process and the formation of the Beilby layer.

Laser induced damage (breakdown) initiated on the exit surface of transparent dielectric materials using nanosecond pulses creates a volume of superheated material reaching localized temperatures on the order of 1 eV and pressures on the order of 10 GPa or larger. This leads to material ejection and the formation of a crater. The volume of this superheated material depends largely on the laser parameters such as fluence and pulse duration. To elucidate the material behaviors involved, we examined the morphologies of the ejected superheated material particles and found distinctive morphologies. We hypothesize that these morphologies arise from the difference in the structure and physical properties (such as the dynamic viscosity and presence of instabilities) of the superheated material at the time of ejection of each individual particle. Some of the ejected particles are on the order of 1 mu m in diameter and appear as "droplets". Another subgroup appears to have stretched, foam-like structure that can be described as material globules interconnected via smaller in diameter columns. Such particles often contain nanometer size fibers attached on their surface. In other cases, only the globules have been preserved suggesting that they may be associated with a collapsed foam structure under the dynamic pressure as it traverses in air. These distinct features originate in the structure of the superheated material during volume boiling just prior to the ejection of the particles.

The design of the National Ignition Facility (NIF) includes a Final Optics Assembly (FOA) subsystem for ultraviolet (UV) light generation and transport for each of the 192 beamlines. Analytical and experimental work has been done to help understand and predict the performance of FOA.

We investigate theoretically the transition from solid dielectric materials to warm solid density plasma during laser-induced breakdown in DKDP crystals (KD2PO4). Evidence taken from the experimentally measured wavelength dependence of the breakdown threshold suggests that the material excitation mechanisms mainly consist of a sequence of one-photon absorptions between short-lived vibronic defect states spanning the band gap with a quasi-continuum of states. The transition between excitation paths involving different number of photons yields information about the role of temperature in determining the width of the transition and corresponding threshold conduction band density prior to initiation of breakdown. This physical system is well adapted to study a plasma warming up at solid density leading to the so-called warm dense matter.

Progress on understanding phenomena influencing surface figure and roughness during pad polishing are reviewed, followed by a description of a new Convergent Polishing process allowing single iteration, process variation-free finishing of optical flats & spheres.