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UCC Library and UCC Researchers Have Made This Item Openly Available UCC Library and UCC researchers have made this item openly available. Please let us know how this has helped you. Thanks! Title Atomic layer deposition of copper – study through density functional theory Author(s) Dey, Gangotri Publication date 2014 Original citation Dey, G. 2014. Atomic layer deposition of copper – study through density functional theory. PhD Thesis, University College Cork. Type of publication Doctoral thesis Rights © 2014, Gangotri Dey. http://creativecommons.org/licenses/by-nc-nd/3.0/ Embargo information No embargo required Item downloaded http://hdl.handle.net/10468/1757 from Downloaded on 2021-10-05T08:22:03Z 0 Atomic Layer Deposition of Copper – Study through Density Functional Theory A thesis presented to the National University of Ireland for the degree of Doctor Of Philosophy in chemistry By Gangotri Dey Under the supervision of Dr. Simon D. Elliott October 2014 Tyndall National Institute (Cork, Ireland) Funded by SFI - Grant 09.IN1.I2628 0 ………When you want something, all the universe conspires in helping you to achieve it – Paulo Coelho (The Alchemist) ……… Nuair atá ní ar bith uait, beidh rath ort le cúnamh na cruinne - Paulo Coelho (The Alchemist) 1 .….To my Parents and Grandparents 2 Declaration: Hereby I Gangotri Dey declare that all the work reported in this thesis is my own. Signature: ------------------------------------------ Date: -------------------------------------------------- 3 Acknowledgement My sincere thanks to Dr. Simon D. Elliott for his supervision during my PhD studies. It has been a great experience working with a perfectionist like him. I have developed better understanding for research activity and learnt proper scientific approach under him. I would also like to thank Prof. Jim Greer, Dr. Michael Nolan, Dr. Damien Thompson (now in UL) for their support. Many thanks to Dr. James Rohan from Tyndall National Institute and Dr. Orla Ni Dhubhghaill from UCC Chemistry Department for being a part of my advisory committee. Dr. Mahdi Shirazi is a great friend and colleague. His motivational speech during those tough times had given me a boost. (Would be Dr.) Yasheng Maimaiti and Merid Legesse has been a good company. Cheers! To all the MMD group members (former ETG), you guys rock. My sincere acknowledgement to Dr. Dirk Hagen, Dr. Lynette Keeney, Dr. Jacqueline Wrench and Prof. Martyn Pemble from AMSG group here in Tyndall National Institute for their contribution in my research project and Roger Nagle, Scott B. Clendenning and Harsono Simka from Intel for their useful discussion during the initial part of my Ph.D. Go raibh maith agat to Science Foundation Ireland (SFI) for funding. Thanks to Ma, Baba and Buchum (my brother). Without you guys I am incomplete. I would like to thank Dr. Biswajit Santra for being a great motivation. Throughout my PhD journey your support was of great help. I am lucky to have you as my partner. Thanks to Dr. Megha Aggarwal, my high school friend. Finally Megha we both can call ourselves Dr.’s in our own way. Cheers to both of us! My sincere gratitude to my teachers from school and college days. They are Dr. Anupa Saha, Dr. Anup Pathak and Dr. Rana Sen from Scottish Church College, Miss Santa Mukherjee from Our Lady Queen Of the Missions and Dr. Krishna Mukherjee from Auxilium Convent School, Kolkata, India. You all trusted me more than I did myself. Thank 4 you to Prof. Anjali Athawale and Prof. S.R. Gadre from Pune University for their inspiration during my Master’s studies. Finally big thanks to my adopted family in Cork. I will restrict the names to few as otherwise the list will make my PhD thesis look thicker. Anushka Gangnaik, Anjana Kulkarni, Santosh Kulkarni, Tuhin Subhra Maity, Dhiman Mallick, Ricky Anthony, Pranay Podder, Preeti Balaji, Nitin Deepak, Sibu, KK, Prasanna, Lehre, Satish, UK, Tayabba and the rest. A special shout out to you Sumreen. I will always love and cherish the moments I had with you guys. You have given me an unforgettable experience here in Cork. 5 Abstract The wonder of the last century has been the rapid development in technology. One of the sectors that it has touched immensely is the electronic industry. There has been exponential development in the field and scientists are pushing new horizons. There is an increased dependence in technology for every individual from different strata in the society. Atomic Layer Deposition (ALD) is a unique technique for growing thin films. It is widely used in the semiconductor industry. Films as thin as few nanometers can be deposited using this technique. Although this process has been explored for a variety of oxides, sulphides and nitrides, a proper method for deposition of many metals is missing. Metals are often used in the semiconductor industry and hence are of significant importance. A deficiency in understanding the basic chemistry at the nanoscale for possible reactions has delayed the improvement in metal ALD. In this thesis, we study the intrinsic chemistry involved for Cu ALD. This work reports computational study using Density Functional Theory as implemented in TURBOMOLE program. Both the gas phase and surface reactions are studied in most of the cases. The merits and demerits of a promising transmetallation reaction have been evaluated at the beginning of the study. Further improvements in the structure of precursors and co- reagent have been proposed. This has led to the proposal of metallocenes as co-reagents and Cu(I) carbene compounds as new set of precursors. A three step process for Cu ALD that generates ligand free Cu layer after every ALD pulse has also been studied. Although the chemistry has been studied under the umbrella of Cu ALD the basic principles hold true for ALD of other metals (e.g. Co, Ni, Fe ) and also for other branches of science like thin film deposition other than ALD, electrochemical reactions, etc. 6 Table of Contents List of Figures: ......................................................................................................................... 10 List of Tables: .......................................................................................................................... 15 Conversions: ............................................................................................................................ 18 Abbreviations ........................................................................................................................... 18 1 Introduction ........................................................................................................................... 21 1.1 What are the latest targets for semiconductor industry? ................................................ 22 1.2 Atomic Layer Deposition (ALD): .................................................................................. 28 1.3 ALD of metals/pure elements: ....................................................................................... 33 1.4 ALD of Cu metal. ........................................................................................................... 39 1.5 Objective of the thesis: ................................................................................................... 46 2. Computational Techniques used .......................................................................................... 48 2.1 The Schrödinger Equation:............................................................................................. 49 2.2 First Principle methods - Density Functional Theory: ................................................... 51 2.3 Basis Sets: ...................................................................................................................... 54 2.4 Molecular Dynamics ...................................................................................................... 55 2.5 Population Analysis: ...................................................................................................... 56 2.6 DFT methods in ALD: ................................................................................................... 57 Chapter 3: Mechanism for the atomic layer deposition of copper using diethylzinc as the reducing agent – a Density Functional Theory study using gas phase molecules as a model . 62 3.1. Introduction ................................................................................................................... 63 3.2. Methods ......................................................................................................................... 66 3.3. Results ........................................................................................................................... 68 3.3.1.a Structure of Cu(II) and Zn(II) compounds ........................................................... 68 3.3.1.b Structure of Cu(I) and Zn(I) compounds .............................................................. 68 3.3.1.c Entropy.................................................................................................................. 72 3.3.2 Reaction Mechanism ............................................................................................... 72 3.4. Discussion ..................................................................................................................... 80 3.4.1 Geometry of the compounds: .................................................................................. 80 3.4.2 Reactions ................................................................................................................. 82 3.5.
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