Abstract

We investigated the crystallinity and optical parameters of silver layers of 10–35 nm thickness as a function 2–10 nm thick Ge wetting films deposited on SiO2 substrates. X-ray reflectometry (XRR) and X-ray diffraction (XRD) measurements proved that segregation of germanium into the surface of the silver film is a result of the gradient growth of silver crystals. The free energy of Ge atoms is reduced by their migration from boundaries of larger grains at the Ag/SiO2 interface to boundaries of smaller grains near the Ag surface. Annealing at different temperatures and various durations allowed for a controlled distribution of crystal dimensions, thus influencing the segregation rate. Furthermore, using ellipsometric and optical transmission measurements we determined the time-dependent evolution of the film structure. If stored under ambient conditions for the first week after deposition, the changes in the transmission spectra are smaller than the measurement accuracy. Over the course of the following three weeks, the segregation-induced effects result in considerably modified transmission spectra. Two months after deposition, the slope of the silver layer density profile derived from the XRR spectra was found to be inverted due to the completed segregation process, and the optical transmission spectra increased uniformly due to the roughened surfaces, corrosion of silver and ongoing recrystallization. The Raman spectra of the Ge wetted Ag films were measured immediately after deposition and ten days later and demonstrated that the Ge atoms at the Ag grain boundaries form clusters of a few atoms where the Ge–Ge bonds are still present.

Highlights

  • Silver is a noble metal with lowest loss in the visible to the near-infrared wavelengths; the surface plasmon polariton (SPP) wave propagation length crucial for plasmonic devices is greatest at Ag/dielectric interfaces [1,2,3]

  • Atomic force microscopy (AFM) scans show that the grain size decreases when the Ag layer is deposited on a Ge wetting film (Figure 2b) with respect to the non wetted film (Figure 2a), which is in consistency with the previous findings [4,19,20,22,24]

  • The Raman spectra show that segregating germanium results in the formation of clusters of a few atoms, where Ge–Ge bonds are preserved

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Summary

Introduction

Silver is a noble metal with lowest loss in the visible to the near-infrared wavelengths; the surface plasmon polariton (SPP) wave propagation length crucial for plasmonic devices is greatest at Ag/dielectric interfaces [1,2,3]. To investigate the kinetics of the segregation process, we perform time-dependent transmission and ellipsometry measurements for Ag samples deposited on Ge films with thicknesses varying from 2 to 10 nm.

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