New precursors for the deposition of Hf02 and ZrO2 by MOCVD and ALD

O'Kane, Ruairi (2007) New precursors for the deposition of Hf02 and ZrO2 by MOCVD and ALD. PhD thesis, University of Liverpool.

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Abstract

Zr02 and Hf02 are two high-pemitivity (lC) dielectric oxides that are currently being investigated as alternatives to Si02 as the dielectric insulating layer in subO. lflm CMOS technolqgy and capacitor layers in .the next generation DRAM. Metal organic chemical vapour deposition (MOCVD) and atomic layer deposition (ALD) are promising techniques for the deposition of the these high-lC dielectric oxides. This study describes the preparation ofnew metal-alkoxides, metallocenes . and ansa-bridged metilllocenes of zirconium and hafnium for use as precursors in MOCVD and ALD. The structure of the metal-alkoxides [Zr(OIBu)2(dmop)2] (1), [Hf(OIBu)2(dmop)2] (2), [Hf(dmop)4] (3), [Hf(OIBu)2(dmoph)2] (4), [Hf2(flr O)(dmoph)6] (7), [Zr(mph)4] (8), [Hf(mph)4] (9), [Hf2(mph)6][(CH3)2NH2] (10) have been determined by single crystal X-ray diffraction (XRD). The preparation of a series of metallocenes of hafnium is described [Cp2HfMe(OMe)] (11), [Cp2HfMe(OEt)] (12), [Cp2HfMe(Oipr)] (13), [Cp2Hf(OMe)2] (14), [Cp2Hf(OEt)2] (15), [Cp2Hf(Oipr)2] (16), [Cp2Hf(OIBu)2] (17), [Cp2Hf(mmp)2] (18), [(Me-Cp)2HfMe(OMe)] (19), [(Me-Cp)2HfMe(OEt)] (20), [(MeCp) 2HfMe(Oipr)] (21), [(Me-Cp)2HfMe(OIBu)] (22), [(Me-Cp)2HfMe(mmp)] (23) and the structure of [Hf(T\5-C5~)2Cl(CH3)] (24) has been determined by single crystal XRD. Chapter 4 describes the synthesis of the. ansa-bridged and hafnium [Zr{H2C(C5~)2}Me2] (25), [Hf{H2C(C5~)2}Me2] (26), [Zr{(CH3)C(C5~)}(CH3)2] (27), and [Hf{(CH3)C(C5~)}(CH3)2] (28). This project involves the investigation of a range new zirconium and hafnium alkoxides and metallocenes with the aim of developing improved MOCVD . and ALD precursors.

Item Type:	Thesis (PhD)
Depositing User:	Symplectic Admin
Date Deposited:	20 Oct 2023 12:41
Last Modified:	20 Oct 2023 12:54
DOI:	10.17638/03174697
Copyright Statement:	Copyright © and Moral Rights for this thesis and any accompanying data (where applicable) are retained by the author and/or other copyright owners. A copy can be downloaded for personal non-commercial research or study, without prior permission or charge.
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3174697