Alkali-resistant low-temperature atomic-layer-deposited oxides for optical fiber sensor overlays

This paper presents an investigation of properties of selected metallic oxides deposited at a low temperature (100 °C) by atomic layer deposition (ALD) technique, relating to their applicability as thin overlays for optical fiber sensors resistant in alkaline environments. Hafnium oxide (Hf_xO_y with y/x approx. 2.70), tantalum oxide (Ta_xO_y with y/x approx. 2.75) and zirconium oxide (Zr_xO_y with y/x approx. 2.07), which deposition was based, respectively, on tetrakis(ethylmethyl)hafnium, tantalum pentachloride and tetrakis(ethylmethyl)zirconium with deionized water, were tested as thin layers on planar Si (100) and glass substrates. Growth per cycle (GPC) in the ALD processes was 0.133–0.150 nm/cycle. Run-to-run GPC reproducibility of the ALD processes was best for Hf_xO_y (0.145 ± 0.001 nm/cycle) and the poorest for Ta_xO_y (0.133 ± 0.003 nm/cycle). Refractive indices n of the layers were 2.00–2.10 (at the wavelength λ = 632 nm), with negligible k value (at λ for 240–930 nm). The oxides examined by x-ray diffractometry proved to be amorphous, with only small addition of crystalline phases for the Zr_xO_y. The surfaces of the oxides had grainy but smooth topographies with root-mean square roughness ∼0.5 nm (at 10 × 10 μm² area) according to atomic force microscopy. Ellipsometric measurements, by contrast, suggest rougher surfaces for the Zr_xO_y layers. The surfaces were also slightly rougher on the glass-based samples than on the Si-based ones. Nanohardness and Young modules were 4.90–8.64 GPa and 83.7–104.4 GPa, respectively. The tests of scratch resistance revealed better tribological properties for the Hf_xO_y and the Ta_xO_y than for the Zr_xO_y. The surfaces were hydrophilic, with wetting angles of 52.5°–62.9°. The planar oxides on Si, being resistive even to concentrated alkali (pH 14), proved to be significantly more alkali-resistive than Al₂O₃. The Ta_xO_y overlay was deposited on long-period grating sensor induced in optical fiber. Thanks to such an overlay the sensor proved to be long-lasting resistant when exposed to alkaline environment with a pH 9. Thereby, it also proved that it has a potential to be repeatedly reused as a regenerable optical fiber biosensor. (paper)