A low-temperature thermal ALD process for nickel utilizing dichlorobis(triethylphosphine)nickel(ii) and 1,4-bis(trimethylgermyl)-1,4-dihydropyrazine

Abstract

In this work, we developed a new ALD process for nickel metal from dichlorobis(triethylphosphine)nickel(II) (NiCl₂(PEt₃)₂) and 1,4-bis(trimethylgermyl)-1,4-dihydropyrazine ((Me₃Ge)₂DHP). A series of phosphine adducts of nickel and cobalt halides were synthesized and characterized for their volatility and thermal stability. Also (Me₃Ge)₂DHP is a novel reducing agent in ALD. Smooth nickel films were deposited on different substrate materials at 110 °C, which is the lowest deposition temperature for Ni metal found in the literature. The growth rate is 0.2 Å per cycle when the film is not continuous and decreases to 0.1 Å per cycle after the film becomes pinhole-free. Besides a small amount (7 at%) of carbidic carbon, the films have only small amounts of impurities. Most notably, the chlorine content is below 0.2 at%, indicating efficient reduction. Furthermore, we think that (Me₃Ge)₂DHP can open new avenues for the ALD of other metals at low temperatures.