The complex refractive index components, n and k, have been studied for thin films of several common dielectric materials with a low to medium refractive index as functions of wavelength and stoichiometry for mid-infrared (MIR) wavelengths within the range 1.54-14.29 μm (700-6500 cm(-1)). The materials silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, and titanium oxide are prepared using room temperature reactive sputter deposition and are characterized using MIR variable angle spectroscopic ellipsometry. The investigation shows how sensitive the refractive index functions are to the O2 and N2 flow rates, and for which growth conditions the materials deposit homogeneously. It also allows conclusions to be drawn on the degree of amorphousness and roughness. To facilitate comparison of the materials deposited in this work with others, the index of refraction was also determined and provided for the near-IR and visible ranges of the spectrum. The results presented here should serve as a useful information base for designing optical coatings for the MIR part of the electromagnetic spectrum. The results are parameterized to allow them to be easily used for coating design.

SummaryWe report on results on the preparation of thin (<100 nm) aluminum oxide (Al2O3) films on silicon substrates using thermal atomic layer deposition (T-ALD) and plasma enhanced atomic layer deposition (PE-ALD) in the SENTECH SI ALD LL system. The T-ALD Al2O3 layers were deposited at 200 °C, for the PE-ALD films we varied the substrate temperature range between room temperature (rt) and 200 °C. We show data from spectroscopic ellipsometry (thickness, refractive index, growth rate) over 4” wafers and correlate them to X-ray photoelectron spectroscopy (XPS) results. The 200 °C T-ALD and PE-ALD processes yield films with similar refractive indices and with oxygen to aluminum elemental ratios very close to the stoichiometric value of 1.5. However, in both also fragments of the precursor are integrated into the film. The PE-ALD films show an increased growth rate and lower carbon contaminations. Reducing the deposition temperature down to rt leads to a higher content of carbon and CH-species. We also find a decrease of the refractive index and of the oxygen to aluminum elemental ratio as well as an increase of the growth rate whereas the homogeneity of the film growth is not influenced significantly. Initial state energy shifts in all PE-ALD samples are observed which we attribute to a net negative charge within the films.

Titanium oxide (TiO2) deposited by atomic layer deposition (ALD) is used as a protective layer in photocatalytic water splitting system as well as a dielectric in resistive memory switching. The way ALD is performed (thermally or plasma-assisted) may change the growth rate as well as the electronic properties of the deposited films. In the present work, the authors verify the influence of the ALD mode on functional parameters, by comparing the growth rate and electronic properties of TiO2 films deposited by thermal (T-) and plasma-enhanced (PE-) ALD. The authors complete the study with the electrical characterization of selected samples by means of capacitance–voltage and current–voltage measurements. In all samples, the authors found a significant presence of Ti3+ states, with the lowest content in the PE-ALD grown TiO2 films. The observation of Ti3+ states was accompanied by the presence of in-gap states above the valence band maximum. For films thinner than 10 nm, the authors found also a strong leakage current. Also in this case, the PE-ALD films showed the weakest leakage currents, showing a correlation between the presence of Ti3+ states and leakage current density.

Spectroscopic ellipsometry is emerging as a routine tool for in-situ and ex-situ thin-film characterization in semiconductor manufacturing. For interconnects in ULSI circuits, diffusion barriers of below 10 nm thickness are required and precise thickness control of the deposited layers is indispensable. In this work, we studied single films of tantalum and two stoichiometries of tantalum nitride as well as TaN/Ta film stacks both on bare and oxidized silicon. Spectroscopic ellipsometry from the UV to the NIR was applied to determine the optical properties of the films for subsequent modeling by a Lorentz-Drude approach. These models were successfully applied to TaN/Ta thin-film stacks where the values of the film thickness could be determined exactly. Moreover, it is shown that considerable differences in the optical properties arise from both film thickness and substrate.

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