Lithography-Free Metaplasmonic Sensors Developed by TWD/GLAD Technique
Authors: Lopez-Munoz Gerardo , Grochala Dominik , Paleczek Anna , Wiącek Mirosław , Kocoń Matuesz , Dudzik Maciej , Rydosz Artur 
Published: August 2024

Nowadays, plasmonic sensors are the most widely used and commercialized label-free optical biosensors and have become a widespread tool for studying chemical/biochemical interactions. Label-free, real-time, and direct measurements are the major benefits of the plasmonic sensors, including high-throughput surface bio-functionalization strategies without amplification or pretreatment of the sample [1]. The working principle of plasmonic sensing has been extensively described and reviewed over the decades [2], however, the possibility to develop cheap, effective, and clinically-accepted biosensors has recently become available due to the development of nanotechnology. Briefly, these nanostructures can be localized or can be arranged on 2D arrays of plasmonic metasurfaces, and can be fabricated by single-layer metallic films and a combination of metallic and dielectric films. The most popular plasmonic metals are gold and silver due to their high conductivity and low dielectric losses. Generally, top-down nanofabrication methods based on laser/e-beam lithography have been used, including nanostencil lithography based on shadow-masked nano-pattering and nanoimprint lithography [3]. Although such technologies have a high potential to achieve scalable and cost-effective nanofabrication at the wafer scale, these processes maintain the following main challenge: a master nano-mold/pattern is required to transfer metasurfaces with an associated high cost. Therefore, other technologies are the subject of research that overcomes this limitation and still offer an outstanding quality of metallic films, such as TDW (thermal dewetting) and GLAD (glancing angle deposition) (Fig.1). These techniques do not require master nano-mold/patterns; consequently, they can achieve lithography-free large-scale plasmonic metasurfaces [4]. TDW and GLAD usually generate quasi-ordered plasmonic metasurfaces compared to conventional lithographic methods.
In this paper, the experimental results of the optical sensing properties of the sensors developed by the utilization of the combination of these two technologies in a single system are presented. The TWD/GLAD magnetron sputtering system has been designed and manufactured based on the Kurt J. Lesker MAG-Torus magnetrons, supplied with DC/RF power sources and an ECR manipulator that enables deposition at various angles with maximal 20 rpm rotation speed and heating option up to 850oC. The system is controlled by the software that enables deposition of the samples with the same parameters which pave the way for fabrication of the sensors on the industrial scale. The optical-sensing system was built based on an ST-VIS-50 spectrometer (Ocean Optics) and Tungsten Halogen Source (360-2000 nm, 2800 K, Ocean Optics) and optical table from Thorlabs. The obtained reflectance measurement has shown that the utilization of the GLAD technique decreases the reflectance peak in comparison with samples deposited without GLAD (flat samples). At the same time, angles in the range of 82-86oC seem to be preferable for nanostructure fabrication.
Additionally, the utilization of the TWD technique, i.e. deposition at lower temperatures in the range of 60-100oC (depending on the substrate) and then annealed at higher temperatures such as 250oC and 300oC in a vacuum and under argon flow in the deposition chamber led to increased normalized response. However, the experiments have shown that the optimal annealing time is between 30-45 min depending on the SPR multi-structure, for example for Ag (6nm), Ti (2nm), and Au (2nm) the 30min at 250oC seems to be the best set. For such compositions, the surface sensitivity (nm/nm) and bulk sensitivity (nm/RIU) are more or less the same - 0.9 and 300, respectively. The obtained results are very promising for developing cheap, rapid, and very effective biosensors for various applications. Therefore, the obtained results seem to be very interesting for the ECS conference audience, for example, the developed Ag/Ti/Au multi-structures can be applied in novel organ-on-a-chip platforms for LADMET (liberations, absorption, distribution, metabolism, excretion, and toxicology) analysis [5].
Fig. 1. Schematic diagram representation of lithography free methods for developing quasi-ordered metamaterials from left to right: Thermal dewetting and glancing angle deposition. The insert shows the chiral plasmonic nanospirals fabrication by glanced angle deposition [4].
References:
[1] LC Oliveira et al., Springer, 2019. ISBN: 9783030174859
[2] VG Kravets et al., Chem. Rev. 2018, 118, 12, 5912–5951. doi.org/10.1021/acs.chemrev.8b00243
[3] M. Zandieh et al., Analytical Biochemistry. 2018, 548, 96-101. doi.org/10.1016/j.ab.2018.02.023
[4] GA López-Muñoz et al., Front. Sens. 2022, 3:945525. doi: 10.3389/fsens.2022.945525
[5] J. Ramon, A. Rydosz, Human Organs-on-a-chip, 2023. ISBN: 9780443153846
The work was financially supported by the National Science Centre, Poland Sonata-BIS project no 2022/46/E/ST7/00008.

Figure 1