Group IV Transition Metal (M = Zr, Hf) Precursors for High-κ Metal Oxide Thin Films

Ga Yeon Lee, Seungmin Yeo, Seong Ho Han, Bo Keun Park, Taeyong Eom, Jeong Hwan Kim, Soo Hyun Kim, Hyungjun Kim, Seung Uk Son, Taek Mo Chung

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)


This paper describes the synthesis of eight novel zirconium and hafnium complexes containing N-alkoxy carboxamidate-type ligands, as potential precursors for metal oxides and atomic layer deposition (ALD) for HfO2. A series of ligands, viz., N-ethoxy-2,2-dimethylpropanamide (edpaH), N-ethoxy-2-methylpropanamide (empaH), and N-methoxy-2,2-dimethylpropanamide (mdpaH), were used to afford complexes Zr(edpa)4 (1), Hf(edpa)4 (2), Zr(empa)4 (3), Hf(empa)4 (4), Zr(mdpa)4 (5), Hf(mdpa)4 (6), ZrCp(edpa)3 (7), and HfCp(edpa)3 (8). Thermogravimetric analysis curves assessed for the evaporation characteristics of complexes 1-8 revealed single-step weight losses with low residues, except for the mdpa-containing complexes. Single-crystal X-ray diffraction studies of 1, 2, 5, and 6 revealed that all the complexes have monomeric molecular structures, with the central metal ion surrounded by eight oxygen atoms from the four bidentate alkoxyalkoxide ligands. Among the complexes prepared, 8 exhibited a low melting point (64 °C), good volatility (1 Torr at 112 °C), high thermal stability, and excellent endurance over 6 weeks at 120 °C. Therefore, an ALD process for the growth of HfO2 was developed using HfCp(edpa)3 (8) as a novel precursor. Furthermore, the HfO2 film exhibited a low capacitance equivalent oxide thickness of ∼1.5 nm, with Jg as low as ∼3 × 10-4 A/cm2 at Vg -1 V in a metal-insulator-semiconductor capacitor (Au/HfO2/p-Si).

Original languageEnglish
Pages (from-to)17722-17732
Number of pages11
JournalInorganic Chemistry
Issue number23
Publication statusPublished - 2021 Dec 6

Bibliographical note

Funding Information:
This research was supported by a grant for the development of smart chemical materials for the IoT devices project through the Korea Research Institute of Chemical Technology (KRICT) of the Republic of Korea (SS2021-20), the Materials and Components Technology Development Program (10080642, Development on precursors for carbon/halogen-free thin film and their delivery system for high-κ/metal gate application) funded by the Ministry of Trade, Industry & Energy (MOTIE, Korea), and the Nano-Material Technology Development Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (NRF-2017M3A7B4049547).

Publisher Copyright:
© 2021 American Chemical Society.

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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