Surface plasmon resonance for in-plane birefringence measurement of anisotropic thin organic film

TL;DR

This paper demonstrates a novel SPR-based method to measure in-plane birefringence of ultrathin organic films with nematic-like ordering, achieving high-resolution results through simulation and experimental calibration.

Contribution

It introduces a calibration approach using SPR to accurately determine in-plane birefringence of ultrathin organic films with nematic-like order, combining simulation and experimental validation.

Findings

Measured birefringence of CdSA and 8CB films as 0.012 and 0.022.

Developed calibration surface relating resonance angle difference to birefringence.

Validated method with X-ray reflectivity and home-built SPR instrument.

Abstract

The measurement of in-plane birefringence ($\Delta{n}$) of ultrathin film is challenging due to a significant deviation of physical properties of materials in ultrathin regime as compared to that in bulk state. Surface plasmon resonance (SPR) phenomenon can be employed to measure change in refractive index of ultrathin film at a very high resolution. This article discusses simulation of SPR phenomenon in Kretschmann configuration for the measurement of $\Delta{n}$ in organic thin film exhibiting nematic-like ordering on the two dimensional gold surface. The distribution of plasmonic field on the gold surface was found to be anisotropic. This suggested that the coupling plasmonic field with that of organic thin film exhibiting nematic-like ordering on the gold surface will be non-isotropic. Therefore, a non-zero difference in resonance angle (RA) was obtained from SPR measurement performed along the optic-axis (OA) and orthogonal to OA of the in-plane nematic ordering ($\Delta\theta$). A calibration surface showing the variation of ($\Delta\theta$) as a function of $\Delta{n}$ and thickness of thin organic film consisting of shape anisotropic tilted molecules exhibiting nematic-like ordering on gold surface was obtained. This calibration surface was employed for the measurement of $\Delta{n}$ of single layer of Langmuir-Blodgett films of cadmium stearate (CdSA) and 4'-octyl-4-biphenylcarbonitrile (8CB) deposited on SPR chips. The thickness of the LB films was estimated using X-ray reflectivity measurement and $\Delta\theta$ was measured using a home built SPR instrument. The $\Delta{n}$ values were found to be 0.012 and 0.022 for ultrathin films of CdSA and 8CB molecules, respectively.