University of Groningen
Properties of organic-inorganic hybrids
Kamminga, Machteld Elizabeth
IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below.
Document Version
Publisher's PDF, also known as Version of record
Publication date: 2018
Link to publication in University of Groningen/UMCG research database
Citation for published version (APA):
Kamminga, M. E. (2018). Properties of organic-inorganic hybrids: Chemistry, connectivity and confinement. Rijksuniversiteit Groningen.
Copyright
Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).
Take-down policy
If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.
Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum.
Properties of Organic-Inorganic Hybrids
Chemistry, Connectivity and Confinement
Book cover: Illustration of a crystal structure consisting of corner- and face-sharing metal-halide octahedra. Cover design by Martin C. Kamminga.
Zernike Institute PhD thesis series 2018-21 ISSN: 1570-1530
ISBN: 978-94-034-0702-9
ISBN: 978-94-034-0701-2 (electronic version)
The work described in this thesis was performed in the research group Solid State Mate-rials for Electronics of the Zernike Institute for Advanced MateMate-rials at the University of Groningen, The Netherlands. This work was supported by The Netherlands Organisation for Scientific Research NWO (Graduate Programme 2013, No. 022.005.006).
Properties of Organic-Inorganic Hybrids
Chemistry, Connectivity and Confinement
Proefschrift
ter verkrijging van de graad van doctor aan de Rijksuniversiteit Groningen
op gezag van de
rector magnificus prof. dr. E. Sterken en volgens besluit van het college voor promoties.
De openbare verdediging zal plaatsvinden op vrijdag 22 juni 2018 om 16:15 uur
door
Machteld Elizabeth Kamminga geboren op 15 september 1991
Promotores
Prof. dr. T.T.M. Palstra Prof. dr. M.A. Loi
Copromotor Dr. G.R. Blake Beoordelingscommissie Prof. dr. G. Palasantzas Prof. dr. C. Pappas Prof. dr. S.J. Clarke
“This is not the center of the universe But it’s where I wanna be” - Eagles
Contents
1 Introduction 1
1.1 Crystal Structures of Organic-Inorganic Hybrid Materials . . . 2
1.2 Properties of Organic-Inorganic Hybrid Materials . . . 7
1.3 Motivation and Research Aim . . . 10
1.4 Outline of this Thesis . . . 11
Bibliography . . . 14
2 Experimental Strategies 19 2.1 Synthesis of Single Crystals . . . 19
2.1.1 Synthesis of Organic Precursor Salts . . . 20
2.1.2 Crystal Growth from Slow Evaporation . . . 21
2.1.3 Layered-Solution Crystal-Growth Technique . . . 21
2.1.4 Crystal Growth of Air-Sensitive Compounds . . . 22
2.2 Patterning Microstructures . . . 23
2.3 X-Ray Diffraction . . . 24
2.3.1 Single-Crystal X-Ray Diffraction Data Collection and Refinement 24 2.3.2 Powder X-ray Diffraction as a Complementary Method . . . 25
2.3.3 The Use of Non-Standard Space Group Settings . . . 26
2.3.4 Dealing with Crystal Twinning . . . 27
2.4 Conclusions . . . 35
Bibliography . . . 36
3 Confinement Effects in Low-Dimensional Lead Iodide Perovskite Hybrids 37 3.1 Introduction . . . 37 3.2 Experimental Techniques . . . 39 3.2.1 Crystal Growth . . . 39 3.2.2 X-Ray Diffraction . . . 40 3.2.3 Photoluminescence Measurements . . . 40 3.2.4 Computational Methods . . . 40
3.3 Results and Discussion . . . 41
3.4 Conclusions . . . 54
Bibliography . . . 56
CONTENTS
4 The Role of Connectivity on Electronic Properties of Lead Iodide
Perovskite-Derived Compounds 59 4.1 Introduction . . . 59 4.2 Experimental Techniques . . . 60 4.2.1 Crystal Growth . . . 60 4.2.2 X-ray Diffraction . . . 61 4.2.3 Computational Methods . . . 61
4.3 Results and Discussion . . . 61
4.4 Conclusions . . . 70
Bibliography . . . 72
Appendix A . . . 74
5 Polar Nature of (CH3NH3)3Bi2I9Perovskite-Like Hybrids 85 5.1 Introduction . . . 85
5.2 Experimental Techniques . . . 87
5.2.1 Crystal Growth . . . 87
5.2.2 Dielectric Measurements . . . 87
5.2.3 Differential Scanning Calorimetry . . . 87
5.2.4 X-Ray Diffraction . . . 88
5.2.5 Computational Methods . . . 88
5.2.6 Absorption Measurements . . . 88
5.3 Results and Discussion . . . 88
5.4 Conclusions . . . 102
Bibliography . . . 104
6 Out-of-Plane Polarization in a Layered Manganese Chloride Hybrid 107 6.1 Introduction . . . 107
6.2 Experimental Techniques . . . 109
6.2.1 Crystal Growth . . . 109
6.2.2 X-Ray Diffraction . . . 109
6.2.3 Calorimetry Measurements . . . 109
6.3 Results and Discussion . . . 109
6.4 Conclusions . . . 117
Bibliography . . . 119
7 Micropatterned 2D Hybrid Perovskite Thin Films with Enhanced Photoluminescence Lifetimes 121 7.1 Introduction . . . 121
7.2 Experimental Techniques . . . 123
7.2.1 Materials Synthesis . . . 123
7.2.2 Preparation of PDMS Stamps . . . 123
7.2.3 Patterning of the Films . . . 123
7.2.4 X-Ray Diffraction . . . 124
7.2.5 Scanning Electron Microscopy . . . 124
7.2.6 Photoluminescence Measurements . . . 124
CONTENTS
7.3 Results and Discussion . . . 124
7.4 Conclusions . . . 135
Bibliography . . . 137
8 The Role of Hypophosphorous Acid on the Synthesis of Tin-Based Organic-Inorganic Hybrids 141 8.1 Introduction . . . 141
8.2 Experimental Techniques . . . 142
8.2.1 Crystal Growth of 2,5-Dimethylaniline Tin Iodide . . . 142
8.2.2 Crystal Growth of 2,5-Dimethylaniline Triiodide . . . 143
8.2.3 X-Ray Diffraction . . . 143
8.3 Results and Discussion . . . 143
8.4 Conclusions . . . 152
Bibliography . . . 154
9 Spin-Singlet Formation in the Spin-Tetramer Layered Organic-Inorganic Hybrid CH3NH3Cu2Cl5 157 9.1 Introduction . . . 157 9.2 Experimental Techniques . . . 158 9.2.1 Crystal Growth . . . 158 9.2.2 X-Ray Diffraction . . . 160 9.2.3 Magnetic Measurements . . . 160
9.3 Results and Discussion . . . 160
9.4 Conclusions . . . 168 Bibliography . . . 170 Appendix B . . . 173 Summary 177 Samenvatting 179 Acknowledgments 181 List of Publications 185
Structures Deposited in the Crystallographic Database 187
CONTENTS
