Sapphire advanced mitigation process: wet etch to expose sub-surface damage and increase laser damage resistance and...

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.