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The etching of ZnO thin films using acetylacetone (Hacac) doses with long exposure times, followed by purging and subsequent exposure to O2 plasma, is studied in a hot-wall reactor using simultaneous in situ spectroscopic ellipsometry and quadrupole mass spectrometry. The static exposure step results in the efficient consumption of Hacac. For each etch cycle, the O2 plasma plays a crucial role in removing unreacted Hacac from the ZnO surface, priming the surface for subsequent Hacac etching. This is confirmed by the production of CO2 during the O2 plasma pulse. The temperature window for etching is established as 220–280 °C with a maximum etch per cycle (EPC) of 0.15 nm/cy. Under these conditions, the Hacac pulse is 2 s long with a 30 s static hold step followed by 5 s O2 plasma step at 300 W power. Statistical analyses of etch data at the granularity level of each cycle reveal the importance of the static hold step in determining EPC. Arrhenius behavior of etching during the hold step reveals a piecewise linear trend with a low temperature (120–200 °C) activation energy (Ea) of 202 meV and a high temperature (200–320 °C) Ea of 32 meV. It is shown that saturation behavior in EPC is pulse time and static hold time dependent. Shorter Hacac pulses (≤1 s) demonstrate saturation behavior for static hold times ∼30 s, longer pulses of Hacac (≥2 s) show no saturation in EPC with static hold times up to 75 s. 

Atomic layer deposition (ALD) of ruthenium (Ru) is being investigated for next generation interconnects and conducting liners for copper metallization. However, integration of ALD Ru with diffusion barrier refractory metal nitrides, such as tantalum nitride (TaN), continues to be a challenge due to its slow nucleation rates. Here, we demonstrate that an ultraviolet-ozone (UV-O3) pretreatment of TaN leads to an oxidized surface that favorably alters the deposition characteristics of ALD Ru from islandlike to layer-by-layer growth. The film morphology and properties are evaluated via spectroscopic ellipsometry, atomic force microscopy, electrical sheet resistance measurements, and thermoreflectance. We report a 1.83 nm continuous Ru film with a roughness of 0.19 nm and a sheet resistance of 10.8 KΩ/□. The interface chemistry between TaN and Ru is studied by x-ray photoelectron spectroscopy. It is shown that UV-O3 pretreatment, while oxidizing TaN, enhances Ru film nucleation and limits further oxidation of the underlying TaN during ALD. An oxygen “gettering” mechanism by TaN is proposed to explain reduced oxygen content in the Ru film and higher electrical conductivity compared to Ru deposited on native-TaN. This work provides a simple and effective approach using UV-O3 pretreatment for obtaining sub-2 nm, smooth, and conducting Ru films on TaN surfaces.