Preparation of plasmonic Au-TiO2 thin films on a transparent polymer substrate

In this work, plasmonic thin films composed of Au nanoparticles embedded in a TiO2 matrix were prepared in a transparent polymer substrate of poly(dimethylsiloxane) (PDMS). The thin films were deposited by reactive DC magnetron sputtering, and then subjected to heat treatment up to 150 °C in order to promote the growth of the Au nanoparticles throughout the TiO2 matrix. The transmittance spectrum of the thin films was monitored in situ during the heat treatment, and the minimum time required to have a defined localized surface plasmon resonance (LSPR) band was about 10 min. The average size of Au nanoparticles was estimated to be about 21 nm—the majority of them are sized in the range 10–40 nm, but also extend to larger sizes, with irregular shapes. The refractive index sensitivity of the films was estimated by using two test fluids (H2O and DMSO), and the average value reached in the assays was 37.3 ± 1.5 nm/RIU, resulting from an average shift of 5.4 ± 0.2 nm. The results show that it is possible to produce sensitive plasmonic Au-TiO2 thin films in transparent polymer substrates such as PDMS, the base material to develop microfluidic channels to be incorporated in LSPR sensing systems.This research was funded by the Portuguese Foundation for Science and Technology (FCT), co-financed by European Regional Development Fund (ERDF), in the framework of the Strategic Funding, grant number UID/FIS/04650/2019; also by the project NANOSENSING, grant number POCI-01-0145-FEDER-016902 and FCT reference PTDC/FIS-NAN/1154/2014; and by the project NANO4BIO, grant number POCI-01-0145-FEDER-032299 and FCT reference PTDC/FIS-MAC/32299/2017.Joel Borges acknowledges the Portuguese Foundation for Science and Technology (FCT) for his Researcher Contract from project NANO4BIO (grant number POCI-01-0145-FEDER-032299 and FCT reference PTDC/FIS-MAC/32299/2017). Diana I. Meira acknowledges FCT for her PhD Scholarship, SFRH/BD/143262/2019. Marco S. Rodrigues acknowledges FCT for his PhD Scholarship, SFRH/BD/118684/2016. Cláudia Lopes acknowledges her post-doctoral fellowship from project NANOSENSING (POCI-01-0145-FEDER-016902 and FCT reference PTDC/FIS-NAN/1154/2014)

Immobilization of streptavidin on a plasmonic Au-TiO2 thin film towards an LSPR biosensing platform

Optical biosensors based on localized surface plasmon resonance (LSPR) are the future of label-free detection methods. This work reports the development of plasmonic thin films, containing Au nanoparticles dispersed in a TiO2 matrix, as platforms for LSPR biosensors. Post-deposition treatments were employed, namely annealing at 400 °C, to develop an LSPR band, and Ar plasma, to improve the sensitivity of the Au-TiO2 thin film. Streptavidin and biotin conjugated with horseradish peroxidase (HRP) were chosen as the model receptor–analyte, to prove the efficiency of the immobilization method and to demonstrate the potential of the LSPR-based biosensor. The Au-TiO2 thin films were activated with O2 plasma, to promote the streptavidin immobilization as a biorecognition element, by increasing the surface hydrophilicity (contact angle drop to 7°). The interaction between biotin and the immobilized streptavidin was confirmed by the detection of HRP activity (average absorbance 1.9 ± 0.6), following a protocol based on enzyme-linked immunosorbent assay (ELISA). Furthermore, an LSPR wavelength shift was detectable (0.8 ± 0.1 nm), resulting from a plasmonic thin-film platform with a refractive index sensitivity estimated to be 33 nm/RIU. The detection of the analyte using these two different methods proves that the functionalization protocol was successful and the Au-TiO2 thin films have the potential to be used as an LSPR platform for label-free biosensors.Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UIDB/04650/2020, UIDB/04050/2020, and UID/EMS/00285/2020, and by the projects NANO4BIO: POCI-01-0145-FEDER-032299, with FCT reference PTDC/FIS-MAC/32299/2017, and CO2Plasmon, with FCT reference EXPL/CTM-REF/0750/2021. Patrícia Pereira-Silva, Diana I. Meira, and Diogo Costa acknowledge FCT for their Ph.D. scholarships, 2020.08235.BD, SFRH/BD/143262/2019, and SFRH/BD/136279/2018, respectively. Augusto Costa-Barbosa also acknowledges FCT for his Ph.D. scholarships SFRH/BD/133513/2017 and COVID/BD/152169/2021. The authors would like to express their gratitude to Nuno P. Barradas (C2TN, University of Lisbon) and Eduardo Alves (IPFN, University of Lisbon) for RBS measurements and analysis

Optimization of Au:CuO thin films by plasma surface modification for high-resolution LSPR gas sensing at room temperature

In this study, thin films composed of gold nanoparticles embedded in a copper oxide matrix (Au:CuO), manifesting Localized Surface Plasmon Resonance (LSPR) behavior, were produced by reactive DC magnetron sputtering and post-deposition in-air annealing. The effect of low-power Ar plasma etching on the surface properties of the plasmonic thin films was studied, envisaging its optimization as gas sensors. Thus, this work pretends to attain the maximum sensing response of the thin film system and to demonstrate its potential as a gas sensor. The results show that as Ar plasma treatment time increases, the host CuO matrix is etched while Au nanoparticles are uncovered, which leads to an enhancement of the sensitivity until a certain limit. Above such a time limit for plasma treatment, the CuO bonds are broken, and oxygen is removed from the film’s surface, resulting in a decrease in the gas sensing capabilities. Hence, the importance of the host matrix for the design of the LSPR sensor is also demonstrated. CuO not only provides stability and protection to the Au NPs but also promotes interactions between the thin film’s surface and the tested gases, thereby improving the nanocomposite film’s sensitivity. The optimized sensor sensitivity was estimated at 849 nm/RIU, which demonstrates that the Au-CuO thin films have the potential to be used as an LSPR platform for gas sensors.This research was sponsored by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UIDB/04650/2020 and by the project CO2Plasmon with reference EXPL/CTM-REF/0750/2021. M.P. acknowledges her Ph.D. Scholarship from FCT, with reference SFRH/BD/137076/2018. Diana I. Meira acknowledges her Ph.D. Scholarship from FCT, with reference SFRH/BD/143262/2019