Interplay of Precursor and Plasma for The Deposition of HfO₂ via PEALD: Film Growth and Dielectric Properties

Abstract HfO 2 thin films are appealing for microelectronic applications such as high‐ κ dielectric layers, memristors, and ferroelectric memory devices. To fulfill the different requirements of each application, the properties of the deposited material need to be tuned accordingly. In this context, plasma‐enhanced atomic layer deposition (PEALD) is a powerful processing route to tailor the properties of HfO 2 thin films, especially at low temperatures. Herein, a comprehensive bottom‐up approach is presented, ranging from the synthesis of molecularly engineered Hf precursors to the development of a HfO 2 PEALD process and a detailed evaluation where plasma can be exploited to tune the dielectric properties. With the example of the newly synthesized bis‐(dialkylamido)‐bis‐(formamidinato) Hf(IV) precursor, [Hf{η 2 ‐( i PrN) 2 CH} 2 (NMe 2 ) 2 ] which is reactive, thermally robust and volatile, successful implementation in a PEALD process for HfO 2 at low temperatures is demonstrated. The typical atomic layer deposition (ALD) characteristics of precursor saturation, linearity, and ALD temperature window are demonstrated with constant growth of 0.7 Å per cycle from 125 to 200 °C, yielding high‐purity layers. The effect of plasma pulse duration on the chemical composition alongside structural, topographical, as well as dielectric properties of the films is investigated. For the latter, the films are incorporated in metal‐insulator semiconductor (MIS) structures.