University of Groningen
Large Scale Modelling of Photo-Excitation Processes in Materials with Application in Organic
Photovoltaics
Izquierdo Morelos, Maria Antonia
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Izquierdo Morelos, M. A. (2019). Large Scale Modelling of Photo-Excitation Processes in Materials with Application in Organic Photovoltaics. University of Groningen.
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Large Scale Modelling of Photo-Excitation
Processes in Materials with Application in Organic
Photovoltaics
Large Scale Modelling of Photo-Excitation Processes in Materials with Application in Organic Photovoltaics
María Antonia Izquierdo Morelos PhD thesis
University of Groningen The Netherlands
Zernike Institute PhD thesis series 2019-16 ISSN: 1570-1530
ISBN: 978-94-034-1639-7 (printed version) ISBN: 978-94-034-1638-0 (electronic version)
The work presented in this thesis was performed in the Theoretical Chemistry group of the Zernike Institute for Advanced Materials at the University of Groningen, The Netherlands, in the Quantum Chemistry of the Excited State University of Valencia, Spain and in the Amsterdam-based company Software for Chemistry & Materials, The Netherlands. This thesis is part of a European Joint Doctorate (EJD) in Theoretical Chemistry and Computational Modelling (TCCM), which was financed under the frame-work of the Innovative Training Netframe-works (ITN) of the MARIE Skłodowska-CURIE Actions (ITN-EJD-642294-TCCM).
08/07/16 14:35
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Cover artwork: “Lightopia” by the Venezuelan artist Carlos Cruz Diez Cover design: Ilse Modder, www.ilsemodder.nl
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Large Scale Modelling of Photo-Excitation
Processes in Materials with Application in Organic
Photovoltaics
PhD thesis
to obtain the degree of PhD of the University of Groningen
on the authority of the Rector Magnificus Prof. E. Sterken
and in accordance with the decision by the College of Deans
and
to obtain the degree of PhD of the University of Valencia on the authority of the
Rector Magnificus Prof. M. V. Mestre Escrivá and in accordance with
the decision by the College of Deans Double PhD Degree
This thesis will be defended in public on Friday 3 May 2019 at 14:30 hours
by
María Antonia Izquierdo Morelos
born on 20 August 1987Supervisors Prof. R. Broer
Prof. A. Sánchez de Merás Co-supervisor
Dr. D. Roca Sanjuán Assessment Committee Prof. L. J. A. Koster Prof. E. Ortí Guillén Prof. M. Swart Prof. T. P. Straatsma
“Your future hasn’t been written yet. No one’s has. Your future is whatever you make it. So make it a good one.”
Table of Contents
Prologue 11
Chapter 1: Fundamentals of Electronic and Optoelectronic Processes 13
1.1. Overview 13
1.2. Organic Photovoltaics 13
1.2.1. Operating Principle 13
1.2.2. Device Architectures 14
1.2.3. Efficiency 15
1.2.4. Materials for D:A BHJs 15
1.2.5. Challenges 18
1.3.Efficiency Losses in Optoelectronics: Radiationless Decay Mechanisms. 19
References 22
Chapter 2: Objectives 27
2.1. General Objective 27
2.2. Specific Objectives 27
Chapter 3: Electronic Structure Methods 29
3.1. Overview 29
3.2. Hartree-Fock Theory and Electron Correlation Methods 30
3.2.1.Hartree-Fock Theory 30
3.2.2. Multi-Determinant Methods and Electron Correlation 33
3.3. Density Functional Theory 37
3.3.1. Kohn-Sham Equations 38
3.4. Time-Dependent Density Functional Theory 39 3.4.1. Linear Response of the Density Matrix 40
3.5. Embedding Models 41
3.5.1. Polarizable Continuum Model 41
3.5.2. Discrete Reaction Field Within the DFT Framework 42 3.6. Conical Intersections: Beyond the BO Approximation 42
References 45
Chapter 4: Extended Implementation of the Discrete Reaction Field Method 49 in the Amsterdam Density Functional Modelling Suite
4.1. Overview 49
4.2. Atomic Charges and Atomic Polarizabilities 50 7
CHAPTER 0. TABLE OF CONTENTS
4.3. Test on Atomic Charges and Atomic Polarizabilities 50
4.4. Improved DRF Inputs for ADF 53
4.4.1. DRF Inputs from the GUI 53
4.4.2. DRF Inputs Coupled to PLAMS 53
References 55
Chapter 5: Calibration of Exchange-Correlation Functionals for Charge Trans- 57
fer States 57
5.1. Overview 57
5.2. Charge Transfer Energy of a D/A Model System 57
5.3. Conclusions 59
References 62
Chapter 6: Theoretical Study of the Charge Transfer Exciton Binding Energy 63 in Semiconductor Materials for Polymer:Fullerene Based Bulk Heterorojuncti-on Solar Cells
Abstract 63
6.1. Introduction 64
6.2. Methods 68
6.3. Results and Discussion 70
6.3.1. Absorption Properties of Photovoltaic Materials 70 6.3.2. Charge Transfer Energy and Exciton Binding Energy in BHJs 73
6.4. Conclusions 79
References 81
Chapter 7: Ab initio Quantum Chemistry Study of Luminescence in ⇡-Conju- 85 gated Compounds with Applications to Optoelectronic Devices
Abstract 85
7.1. Introduction 86
7.2. Methods 90
7.3. Results and Discussion 91
7.3.1. Ethene, Styrene and Stilbene 91
7.3. 2. DSB,↵-DMDCS, -DMDCS, ↵-TFDCS and -TFDCS 96
7.4. Conclusions 103
References 105
Chapter 8: Outlook and Perspective 109
8.1. Overview 109
8.2. Implementation of QM/DRF Energy Gradients in ADF 109 8.3. Electronic Couplings in D:A OPVs via NOCI 110
References 112
Chapter 9: Conclusions 113
Appendix A 115
CHAPTER 0. TABLE OF CONTENTS Appendix B 121 Summary 133 Samenvatting 137 Resumen 141 List of Acronyms 151 Curriculum Vitae 155 Acknowledgments 159 9
CHAPTER 0. TABLE OF CONTENTS :)
Prologue
Organic photovoltaics represent a highly attractive choice of power generation in terms of cost and flexibility. However, the low efficiencies attained up to now limit their significant application. Such limitation has certainly stimulated fundamental research focused on materials design and device architectures. This dissertation,Large Scale Modelling of Photo-Excitation Processes in Materials with Application in Or-ganic Photovoltaics, investigates -using first principles theory and modelling- more efficient optoelectronic materials. New materials with promising applications in the field are proposed. Special attention is given to electron transfer processes in very large systems and to the prediction of non-radiative mechanisms that contribute to efficiency losses.
This thesis intends to be reader friendly, thus, it is structured in such a way that each Chapter is self-contained (although at the end of this manuscript a list of acronyms is presented). Chapter 1 provides the background for studying the photovoltaic and optoelectronic processes in organic photovoltaics. The state-of-the-art and the current challenges in the field are also described. Chapter 2 outlines the general objective and then it goes through the specific goals. Chapter 3 introduces the theoretical and computational methodologies used along this thesis. Methodologies are only briefly explained. A list of references is provided in case more details are required. Chapter 4 reports the software development contribution of this work. The extended implemen-tation of a polarizable force field, which is part of the Amsterdam Density Functional modeling suite released in 2017, is described. Chapter 5 describes a calibration of exchange-correlation functionals for density functional theory-based methods as the basis for the next Chapter. Chapter 6 studies the charge transfer exciton binding ener-gies in organic semiconductor materials for polymer:fullerene bulk heterojunction solar cells, and consists of a scientific paper published in the Journal of Physical Chem-istry A. Chapter 7 explores the potential energy surfaces of optoelectronic materials, and it is part of a scientific paper in preparation at the time of the thesis submission. Chapter 8 suggests further research lines connected to this project. Chapter 9 closes with the main achievements and general conclusions. For completeness, supplementary appendices and transferable academic achievements are presented.
This thesis is part of a European Joint Doctorate (EJD) in Theoretical Chem-istry and Computational Modelling (TCCM) of the University of Groningen (UG) and 11
CHAPTER 0. PROLOGUE the University of Valencia (UV), in collaboration with the Software for Chemistry & Materials (SCM) company based in Amsterdam, financed by the Innovative Training Networks (ITN) of the MARIE Skłodowska-CURIE Actions (ITN-EJD-642294-TCCM).
