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Advanced Precursor Design for Atomic Layer Deposition and Chemical Vapour Deposition of Gold Metal

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Advanced Precursor Design for Atomic Layer Deposition and Chemical Vapour Deposition of Gold Metal Advanced precursor design for atomic layer deposition and chemical vapour deposition of gold metal by Matthew Bertram Edward Griffiths A thesis submitted to the Faculty of Graduate and Postdoctoral Affairs in partial fulfillment of the requirements for the degree of Doctor of Philosophy In Chemistry Carleton University Ottawa, Ontario © 2020 Matthew Bertram Edward Griffiths This thesis is dedicated to my family ii Abstract This thesis first outlines the current state-of-the-art of gold CVD and ALD precursors based on their precursor figures of merit (σ) which was a concept developed in this research program. Then, this thesis demonstrates the ability to control the structure of deposited nanoparticles by CVD, using a combination of thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) to elucidate the mechanism of growth. This represents one of the first gold CVD studies to rationally design a precursor that would deposit anisotropic nanostructures. This thesis then describes the first gold ALD process (PMe3)AuMe3. Then, a new process using this same precursor and hydrogen plasma was developed and the surface mechanism of this new ALD process was investigated using a combination of in-situ reflection absorption infrared spectroscopy (RAIRS), XPS, and quadrupole mass spectrometry (QMS). This mechanistic study provides insight on the kinetics of Me and PMe3 ligand desorption from the surface and re-defines the upper limit of the Au ALD process. In order to improve on the existing state-of-the-art of gold precursors, this thesis then describes a systematic gold(I) precursor design. Using a combination of TGA, differential scanning calorimetry (DSC), x-ray crystallography, and density functional theory (DFT), we delineate why certain ligands work well for gold(I) and we develop the precursor figure of merit (σ) in this chapter. With a knowledge of the design factors that make a good precursor from the standpoint of thermolysis, this thesis then describes a study where the rate of CVD of various gold(I) precursors is compared by in situ monitoring using a combination of quartz crystal microbalance (QCM) and quadrupole mass spectrometry (QMS). This study culminates in a new idea in the field of ALD: the rational design of a kinetically limited ALD process. We then show that the kinetic implications of steric bulk that are ubiquitous in solution-phase synthetic chemistry can also be exploited in the fields of CVD and ALD. Finally, this thesis describes a study where an alkylgold(I) NHC self-limiting precursor is rationally designed. A family of these types of precursors is presented, and the self-limiting capability of these precursors is demonstrated using our in-situ QCM/QMS monitoring apparatus. We then show that highly conductive and high-purity gold thin films can be deposited with one of these new precursors, and the film’s purity (>99% by XPS) and resistivity (4.2 µΩ cm) rival the current state of the art of Au ALD films. Altogether, this thesis demonstrates that the rational design of deposition precursors is essential to the advancement of the fields of CVD and ALD not only for the development of new processes, but also because of the importance of the precursor on growth morphology. Being able to tailor a compound for a specific thin film material is important not only for gold thin films, but also for the rest of the periodic table, as well as new materials that have not yet been synthesized. iii Preface This preface provides full bibliographical details for each article included in this thesis, as well as whether the article is reproduced in whole or in part. Use of copyrighted material is likewise acknowledged here. When citing material from this thesis, please the cite the article relevant to the chapter, if the chapter is based on a publication. Pursuant to the Integrated Thesis Policy of Carleton University, the supervisor (Dr. Seán T. Barry) and the “student” (Matthew B. E. Griffiths) confirm that the student was fully involved in setting up and conducting the research, obtaining data and analyzing results, as well as preparing and writing the material presented in the co-authored article(s) integrated in the thesis. Additionally, the supervisor confirms the information provided by the student in this preface. Chapter 2 Matthew B. E. Griffiths*, Peter G. Gordon, Zachary S. Dubrawski, and Seán T. Barry, Literature review and figure of merit analysis of gold CVD and ALD precursors, 2020 This literature review would not have been completed if not for the help of Peter G. Gordon and Zachary S. Dubrawski. Matthew B. E. Griffiths researched, extracted data from literature, tabulated, performed figure of merit analysis of the precursors, and wrote the manuscript. Peter G. Gordon and Zachary S. Dubrawski canvassed, categorized, and summarized literature on gold CVD and ALD precursors during the preliminary stages of writing the review. Seán T. Barry supervised MBEG, PGG, and ZSD. Chapter 3 Matthew B. E. Griffiths*, Sara E. Koponen, David J. Mandia, Jennifer F. McLeod, Jason P. Coyle, Jeffrey J. Sims, Javier B. Giorgi, Eric R. Sirianni, Glenn P. A. Yap, and Seán T. Barry, Surfactant-directed growth of gold metal nanoplates by chemical vapor deposition, Chem. Mater., 2015, 27, 6116-6124 This article is wholly reproduced and edited for formatting and clarity of presentation. Matthew B. E. Griffiths performed work related to synthesis and characterization of compounds, chemical vapour deposition experiments, and wrote the manuscript in collaboration with Sara E. Koponen and Seán T. Barry. S. Sara E. Koponen performed work related to synthesis and characterization of compounds and chemical vapour deposition experiments and was closely involved in the writing of the manuscript. David J. Mandia performed XPS analysis of the deposited films and was aided by Jeffrey J. Sims who was supervised by Javier B. Giorgi. Jennifer F. McLeod aided in chemical vapour deposition experiments. Jason P. Coyle synthesized and provided crystallographic data for the compounds included in the manuscript. Crystallography was iv preformed by Eric R. Sirianni and Glenn P. A. Yap. Seán T. Barry supervised MBEG, SEK, DJM, JFM and JPC. Chapter 4 Griffiths, M.B.E., Pallister, P.J., Mandia, D.J., and Barry, S.T.*, Atomic Layer Deposition of Gold Metal, Chem. Mater., 2016, 28, 44-46 This article is wholly reproduced and edited for formatting and clarity of presentation. Matthew B. E. Griffiths performed synthesis, thermolysis and characterization of (PMe3)AuMe3, developed the atomic layer deposition process, and performed SEM imaging and thickness measurements. Peter J. Pallister performed atomic layer deposition experiments, aided in thickness measurements, and collected TEM images. David J. Mandia performed XPS measurements on the deposited films. Seán T. Barry wrote the manuscript in collaboration with Matthew B. E. Griffiths and supervised MBEG, PJP, and DJM. Michiel Van Daele, Matthew B. E. Griffiths, Ali Raza, Matthias Minjauw, Eduardo Solano, Ji-Yu Feng, Ranjith K. Ramachandran, Stéphane Clemmen, Roel Baets, Seán T. Barry, Christophe Detavernier, and Jolien Dendooven*, Plasma-Enhanced Atomic Layer Deposition of Nanostructured Gold Near Room Temperature, ACS Appl. Mater. Interfaces, 2019, 11, 37229-38 This unpublished article is partially reproduced and edited for formatting and clarity of presentation. Michiel Van Daele performed ALD studies, characterized the thin films, and wrote the manuscript. Matthew B. E. Griffiths performed synthesis, thermolysis and characterization of the gold precursors, and helped interpret results obtained by MVD. Michiel Van Daele, Matthew B. E. Griffiths, Matthias Minjauw, Seán T. Barry, Christophe Detavernier, and Jolien Dendooven*, Reaction mechanism of the Me3AuPMe3-H2 plasma-enhanced ALD process, Phys. Chem. Chem. Phys., 2020, 22, 11903 This article is partially reproduced and edited for formatting and clarity of presentation. Michiel Van Daele performed ALD studies, characterized the thin films, and wrote the manuscript. Matthew B. E. Griffiths performed synthesis, thermolysis and characterization of the gold precursors, and helped interpret results obtained by MVD. Chapter 5 Matthew B. E. Griffiths*, Zachary S. Dubrawski, Goran Bačić, Achini Japahuge, Prof. Jason D. Masuda, Prof. Tao Zeng, and Prof. Seán T. Barry, Controlling thermal stability v and volatility of organogold(I) compounds for vapor deposition with complementary ligand design, European Journal of Inorganic Chemistry, 2019, 46, 4927-38 This article is wholly reproduced and edited for formatting and clarity of presentation. Matthew B. E. Griffiths performed synthesis, thermolysis and characterization of all compounds, developed the figure of merit equation, and wrote the manuscript in collaboration with Seán T. Barry. Zachary S. Dubrawski performed on synthesis, thermolysis and characterization of all compounds. Goran Bačić performed some thermolysis experiments and helped develop the figure of merit equation. Achini Japahuge performed DFT experiments and was supervised by Prof. Tao Zeng. Prof. Jason D. Masuda performed crystallography experiments. Seán T. Barry supervised MBEG, ZSD, and GB. Chapter 6 Matthew B. E. Griffiths* and Seán T. Barry, In-situ monitoring of the chemisorption behavior of gold vapour deposition precursors and preliminary assessment of a potential kinetically-limited ALD precursor, Manuscript in preparation Matthew B. E. Griffiths developed the grounding hypothesis,
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