Towards Real-Time In-Situ Mid-Infrared Spectroscopic Ellipsometry in Polymer Processing

Recent developments in mid-infrared (MIR) spectroscopic ellipsometry enabled by quantum cascade lasers (QCLs) have resulted in a drastic improvement in signal-to-noise ratio compared to conventional thermal emitter based instrumentation. Thus, it was possible to reduce the acquisition time for high-resolution broadband ellipsometric spectra from multiple hours to less than 1 s. This opens up new possibilities for real-time in-situ ellipsometry in polymer processing. To highlight these evolving capabilities, we demonstrate the benefits of a QCL based MIR ellipsometer by investigating single and multilayered polymer films. The molecular structure and reorientation of a 2.5 µm thin biaxially oriented polyethylene terephthalate film is monitored during a stretching process lasting 24.5 s to illustrate the perspective of ellipsometric measurements in dynamic processes. In addition, a polyethylene/ethylene vinyl alcohol/polyethylene multilayer film is investigated at a continuously varying angle of incidence (0∘– 50∘) in 17.2 s, highlighting an unprecedented sample throughput for the technique of varying angle spectroscopic ellipsometry in the MIR spectral range. The obtained results underline the superior spectral and temporal resolution of QCL ellipsometry and qualify this technique as a suitable method for advanced in-situ monitoring in polymer processing.

Characterization of thin films from reflection and transmission ellipsometric parameters

Spectroscopic ellipsometry is a powerful tool for characterization of thin films / surfaces. To simultaneously extract optical constant and film thickness from ellipsometric parameters ψ and Δ, dispersion models of material’s refractive index and spectroscopic ellipsometry measurement have been often required. In this work, we propose an extraction method of optical parameters of thin films from the reflection and transmission ellipsometric parameters. This method necessitates neither spectroscopic information of ψ and Δ, nor dispersion models. Verification measurements were carried out with the single-point and imaging ellipsometers, respectively.

Application of Tamm Plasmon Polaritons and Cavity Modes for Biosensing in the Combined Spectroscopic Ellipsometry and Quartz Crystal Microbalance Method

Low-cost 1D plasmonic photonic structures supporting Tamm plasmon polaritons and cavity modes were employed for optical signal enhancement, modifying the commercially available quartz crystal microbalance with dissipation (QCM-D) sensor chip in a combinatorial spectroscopic ellipsometry and quartz microbalance method. The Tamm plasmon optical state and cavity mode (CM) for the modified mQCM-D sample obtained sensitivity of ellipsometric parameters to RIU of ΨTPP = 126.78 RIU−1 and ΔTPP = 325 RIU−1, and ΨCM = 264 RIU−1 and ΔCM = 645 RIU‑1, respectively. This study shows that Tamm plasmon and cavity modes exhibit about 23 and 49 times better performance of ellipsometric parameters, respectively, for refractive index sensing than standard spectroscopic ellipsometry on a QCM-D sensor chip. It should be noted that for the optical biosensing signal readout, the sensitivity of Tamm plasmon polaritons and cavity modes are comparable with and higher than the standard QCM-D sensor chip. The different origin of Tamm plasmon polaritons (TPP) and cavity mode (CM) provides further advances and can determine whether the surface (TPP) or bulk process (CM) is dominating. The dispersion relation feature of TPP, namely the direct excitation without an additional coupler, allows the possibility to enhance the optical signal on the sensing surface. To the best of our knowledge, this is the first study and application of the TPP and CM in the combinatorial SE-QCM-D method for the enhanced readout of ellipsometric parameters.