Research Collection Doctoral Thesis Novel Pb(II), Sn(II) and Bi(III) Halide Semiconductors Author(s): Nazarenko, Olga Publication Date: 2019-04 Permanent Link: https://doi.org/10.3929/ethz-b-000338638 Rights / License: In Copyright - Non-Commercial Use Permitted This page was generated automatically upon download from the ETH Zurich Research Collection. For more information please consult the Terms of use. ETH Library Dissertation ETH No. 25772 Novel Pb(II), Sn(II) and Bi(III) Halide Semiconductors A thesis submitted to attain the degree of DOCTOR OF SCIENCES of ETH ZÜRICH (Dr. sc. ETH Zürich) Presented by Olga Nazarenko Master of Science in Chemistry Kiev National Taras Shevchenko University Born on 26.12.1989 Citizen of Ukraine Accepted on the recommendation of Prof. Dr. Maksym V. Kovalenko, examiner Prof. Dr. Hansjörg Grützmacher, co-examiner Department of Chemistry and Applied Biosciences Laboratory of Inorganic Chemistry 2019 Declaration | Olga Nazarenko Declaration I hereby confirm that I am the sole author of the written work herein enclosed and that I have compiled it in my own words. Parts excepted are corrections of form and content by the supervisor. Title of work: Novel Pb(II), Sn(II) and Bi(III) halide semiconductors With my signature I confirm: − I have committed none of the forms of plagiarism. − I have documented all methods, data, and processes truthfully. − I have not manipulated any data. − I have mentioned all persons who were significant contributors to this work, as described below. − I obtained copyright permissions from the journal for reproducing the text and Figures in this thesis, where needed. − I am aware that the work may be screened electronically for plagiarism. Place, date Signature(s) Dr. S. Yakunin (ETH Zürich) performed the TR-PL, temperature-dependent PL, and photoconductivity measurements, as well as γ-rays detection measurements presented in Chapters 3-7 as well as contributed to the analysis of the data. Dr. E. Cuervo-Reyes (Empa) performed a computational study included in Chapter 4. Dr. M. D. Wörle (ETH Zürich) helped with the crystal structure determination of the compounds presented throughout this thesis. M. Aebli (ETH Zürich) performed SSNMR measurements and contributed to the analysis of the data presented in Chapter 5. L. Piveteau (ETH Zürich) performed SSNMR measurements and contributed to the analysis of the data presented in Chapters 4 and 7. B. M. Benin (ETH Zürich) synthesized Cs8Sn6Br13I7 and characterized it with absorption and powder XRD techniques presented in Chapter 6. Dr. G. Raino (ETH Zürich) performed PL and TR-PL with spatial resolution measurements presented in Chapter 5 and temperature-dependent PL measurements included in Chapter 6. Dr. M. R. Kotyrba (ETH Zürich) carried out a part of the SC-XRD measurements presented in Chapters 4, 5 and contributed to the analysis of the results shown in Chapters 4-6. Dr. F. Krumeich (ETH Zürich) conducted SEM, EDXS measurements presented in Chapter 7. Dr. M. Kepenekian (ISCR, CNRS, Rennes), Prof. Dr. J. Even (INSA, CNRS, Rennes), Dr. Sc. C. Katan (ISCR, CNRS, Rennes) conducted a computational study included in Chapter 6. Dr. Y. Polyhach (ETH Zürich) performed EPR measurements for the project presented in Chapter 7. i Declaration | Olga Nazarenko V. Morad, I. Cherniukh (ETH Zürich) grew some of the single crystals used for the γ-rays detection study, presented in Chapter 3. ii Aknowledgements | Olga Nazarenko Acknowledgments Countless words of gratitude I would like to address to my supervisor Prof. Maksym V. Kovalenko for giving me an opportunity to work and study in his team, for his support and understanding, his supervision, guidance, and a good sense of humor. It was a pleasure to work and to grow in his group. I want to thank all the group members for creating a warm and pleasant atmosphere in the group. Special thanks to Dr. Loredana Protesescu, Dr. Maryna I. Bodnarchuk and Dr. Dmitry Dirin for teaching me the techniques of the colloidal synthesis when I came to the group. I think this is an excellent tradition in Prof. Kovalenko’s group that a newcomer can be taught all sorts of synthetic techniques used in the group. The transfer of knowledge gives a broader scope of possibilities for a new student to develop his pathway in the world of chemistry. I am grateful for the chance bestowed on me to make doctoral studies in the group of Prof. Maksym Kovalenko at ETH Zurich. The creative and supportive atmosphere at ETH Zurich makes it to a perfect place for effective learning and personal development. I want further to express my gratitude to Dr. Michel D. Wörle, who taught me so much about the X-ray diffraction. I am thankful for his patience, help, and support throughout my Ph.D.. As well as I am grateful to Michael for keeping the Smart in an excellent condition, as on this rather old device I could perform numerous single crystal XRD measurements. Special thanks to Sergii Yakunin for all his amusing life stories during coffee breaks, as well as for his support and collaboration. Through different periods of my Ph.D., I got to work with many people, with various devices, different synthetic techniques. Some of the most challenging things were welding of metal ampules, sealing quartz ampules, working with liquid ammonia. For these incredible skills and knowledge, I am gratified to Dr. Martin R. Kotyrba. I am grateful to my supporting and loving family for believing in me and to my boyfriend Martin for being there for me, for his encouragement, inspiration, funny chemistry related stories, and for bringing balance into my life. I want to thank Claudia Salameh-Ott and Chantal Hänni for support with administrative matters. I thank Prof. Dr. Hansjörg Grützmacher for his kind willingness to co-examine this thesis. Last but not least, I would like to thank the members of the examination committee for their efforts and time and also to you, the reader, for considering my work. iii Table of Contents | Olga Nazarenko Table of Contents Declaration ...................................................................................................................... i Acknowledgments ......................................................................................................... iii Abbreviations ................................................................................................................ vi Summary ..................................................................................................................... viii Zusammenfassung ......................................................................................................... xi Chapter 1. Introduction .......................................................................................................1 1.1. A brief history of semiconductors ...............................................................................1 1.2. Mixed organic-inorganic lead halide perovskites: basics and properties ......................3 1.3. Bandgap theory of semiconductors .............................................................................8 1.4. The defect tolerance ................................................................................................. 11 1.5. Layered lead halide perovskites ................................................................................ 13 1.6. The potential applications of LHPs ........................................................................... 16 1.7. On Sn(II) and Ag(I)/Bi(III) halide compounds with perovskite crystal structure ....... 19 1.8. Scope and outline of the dissertation ......................................................................... 22 Chapter 2. Methods and techniques .................................................................................. 26 2.1. The growth of single crystals .................................................................................... 26 2.2. Characterization methods ......................................................................................... 28 Chapter 3. Single crystals of caesium-formamidinium lead halide perovskites: solution growth and gamma dosimetry ............................................................................................... 34 3.1. Introduction .............................................................................................................. 34 3.2. Experimental section ................................................................................................ 36 3.3. Results and discussion .............................................................................................. 38 3.4. Conclusions .............................................................................................................. 47 Chapter 4. Luminescent and photoconductive layered lead halide perovskite compounds comprising mixtures of caesium and guanidinium cations ..................................................... 49 4.1. Introduction .............................................................................................................. 49 4.2. Experimental section ................................................................................................ 51 4.3. Results and discussion .............................................................................................. 55 4.4. Conclusions .............................................................................................................. 69 Chapter 5. Guanidinium-formamidinium lead iodide: a layered