Atomic Layer Deposition of Intermetallic Fe₄Zn₉ Thin Films from Diethyl Zinc

We present a new type of atomic layer deposition (ALD) process for intermetallic thin films, where diethyl zinc (DEZ) serves as a coreactant. In our proof-of-concept study, FeCl₃ is used as the second precursor. The FeCl₃ + DEZ process yields in situ crystalline Fe₄Zn₉ thin films, where the elemental purity and Fe/Zn ratio are confirmed by time-of-flight elastic recoil detection analysis (TOF-ERDA), Rutherford backscattering spectrometry (RBS), atomic absorption spectroscopy (AAS), and energy-dispersive X-ray spectroscopy (EDX) analyses. The film thickness is precisely controlled by the number of precursor supply cycles, as expected for an ALD process. The reaction mechanism is addressed by computational density functional theory (DFT) modeling. We moreover carry out preliminary tests with CuCl₂ and Ni(thd)₂ in combination with DEZ to confirm that these processes yield Cu−Zn and Ni−Zn thin films with DEZ as well. Thus, we envision an opening of a new ALD approach based on DEZ for intermetallic/metal alloy thin films.