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 x O y with y/x approx. 2.70), tantalum oxide (Ta x O y with y/x approx. 2.75) and zirconium oxide (Zr x O 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 x O y (0.145 ± 0.001 nm/cycle) and the poorest for Ta x O 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 x O 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 x O 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 x O y and the Ta x O y than for the Zr x O 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 x O 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.

Titanium oxide thin films obtained with physical and chemical vapour deposition methods for optical biosensing purposes.

This work discusses an application of titanium oxide (TiOx) thin films deposited using physical (reactive magnetron sputtering, RMS) and chemical (atomic layer deposition, ALD) vapour deposition methods as a functional coating for label-free optical biosensors. The films were applied as a coating for two types of sensors based on the localised surface plasmon resonance (LSPR) of gold nanoparticles deposited on a glass plate and on a long-period grating (LPG) induced in an optical fibre. Optical and structural properties of the TiOx thin films were investigated and discussed. It has been found that deposition method has a significant influence on optical properties and composition of the films, but negligible impact on TiOx surface silanization effectiveness. A higher content of oxygen with lower Ti content in the ALD films leads to the formation of layers with higher refractive index and slightly higher extinction coefficient than for the RMS TiOx. Moreover, application of the TiOx film independently on deposition method enables not only for tuning of the spectral response of the investigated biosensors, but also in case of LSPR for enhancing the ability for biofunctionalization, i.e., TiOx film mechanically protects the nanoparticles and induces change in the biofunctionalization procedure to the one typical for oxides. TiOx coated LSPR and LPG sensors with refractive index sensitivity of close to 30 and 3400nm/RIU, respectively, were investigated. The ability for molecular recognition was evaluated with the well-known complex formation between avidin and biotin as a model system. The shift in resonance wavelength reached 3 and 13.2nm in case of LSPR and LPG sensors, respectively. Any modification in TiOx properties resulting from the biofunctionalization process can be also clearly detected.

Molecular monolayers on silicon as substrates for biosensors.

(111) silicon surfaces can be controlled down to atomic level and offer a remarkable starting point for elaborating nanostructures. Hydrogenated surfaces are obtained by oxide dissolution in hydrofluoric acid or ammonium fluoride solution. Organic species are grafted onto the hydrogenated surface by a hydrosilylation reaction, providing a robust covalent Si-C bonding. Finally, probe molecules can be anchored to the organic end group, paving the way to the elaboration of sensors. Fluorescence detection is hampered by the high refractive index of silicon. However, improved sensitivity is obtained by replacing the bulk silicon substrate by a thin layer of amorphous silicon deposited on a reflector. The development of a novel hybrid SPR interface by the deposition of an amorphous silicon-carbon alloy is also presented. Such an interface allows the subsequent linking of stable organic monolayers through Si-C bonds for a plasmonic detection. On the other hand, the semiconducting properties of silicon can be used to implement field-effect label-free detection. However, the electrostatic interaction between adsorbed species may lead to a spreading of the adsorption isotherms, which should not be overlooked in practical operating conditions of the sensor. Atomically flat silicon surfaces may allow for measuring recognition interactions with local-probe microscopy.