Lucie McGovern

Bio: Lucie McGovern is an academic researcher from McGill University. The author has contributed to research in topics: Perovskite (structure) & Halide. The author has an hindex of 8, co-authored 10 publications receiving 321 citations.

Quantification of ion migration in CH3NH3PbI3 perovskite solar cells by transient capacitance measurements

Abstract: Ion migration in halide perovskite films leads to device degradation and impedes large scale commercial applications. We use transient ion-drift measurements to quantify activation energy, diffusion coefficient, and concentration of mobile ions in methylammonium lead triiodide (MAPbI3) perovskite solar cells, and find that their properties change close to the tetragonal-to-orthorhombic phase transition temperature. We identify three migrating ion species which we attribute to the migration of iodide (I−) and methylammonium (MA+). We find that the concentration of mobile MA+ ions is one order of magnitude higher than the one of mobile I− ions, and that the diffusion coefficient of mobile MA+ ions is three orders of magnitude lower than the one for mobile I− ions in our samples. This quantification of mobile ions in MAPbI3 will lead to a better understanding of ion migration and its role in operation and degradation of perovskite solar cells.

Understanding the Stability of MAPbBr3 versus MAPbI3: Suppression of Methylammonium Migration and Reduction of Halide Migration

Abstract: Solar cells based on metal halide perovskites often show excellent efficiency but poor stability. This degradation of perovskite devices has been associated with the migration of mobile ions. MAPbBr3 perovskite materials are significantly more stable under ambient conditions than MAPbI3 perovskite materials. In this work, we use transient ion drift to quantify the key characteristics of ion migration in MAPbBr3 perovskite solar cells. We then proceed to compare them with those of MAPbI3 perovskite solar cells. We find that in MAPbBr3, bromide migration is the main process at play and that contrary to the case of MAPbI3, there is no evidence for methylammonium migration. Quantitatively, we find a reduced activation energy, a reduced diffusion coefficient, and a reduced concentration for halide ions in MAPbBr3 compared to MAPbI3. Understanding this difference in mobile ion migration is a crucial step in understanding the enhanced stability of MAPbBr3 versus MAPbI3.

Lattice Compression Increases the Activation Barrier for Phase Segregation in Mixed-Halide Perovskites.

Abstract: The bandgap tunability of mixed-halide perovskites makes them promising candidates for light-emitting diodes and tandem solar cells. However, illuminating mixed-halide perovskites results in the fo...

Supramolecular Modulation of Hybrid Perovskite Solar Cells via Bifunctional Halogen Bonding Revealed by Two-Dimensional 19F Solid-State NMR Spectroscopy

Abstract: There has been an ongoing effort to overcome the limitations associated with the stability of hybrid organic-inorganic perovskite solar cells by using different organic agents as additives to the perovskite formulations. The functionality of organic additives has been predominantly limited to exploiting hydrogen-bonding interactions, while the relevant atomic-level binding modes remain elusive. Herein, we introduce a bifunctional supramolecular modulator, 1,2,4,5-tetrafluoro-3,6-diiodobenzene, which interacts with the surface of the triple-cation double-halide perovskite material via halogen bonding. We elucidate its binding mode using two-dimensional solid-state 19F NMR spectroscopy in conjunction with density functional theory calculations. As a result, we demonstrate a stability enhancement of the perovskite solar cells upon supramolecular modulation, without compromising the photovoltaic performances.

Grain Size Influences Activation Energy and Migration Pathways in MAPbBr3 Perovskite Solar Cells.

Abstract: Ion migration in perovskite layers can significantly reduce the long-term stability of the devices. While perovskite composition engineering has proven an interesting tool to mitigate ion migration, many optoelectronic devices require a specific bandgap and thus require a specific perovskite composition. Here, we look at the effect of grain size to mitigate ion migration. We find that in MAPbBr3 solar cells prepared with grain sizes varying from 2 to 11 μm the activation energy for bromide ion migration increases from 0.17 to 0.28 eV. Moreover, we observe the appearance of a second bromide ion migration pathway for the devices with largest grain size, which we attribute to ion migration mediated by the bulk of the perovskite, as opposed to ion migration mediated by the grain boundaries. Together, these results suggest the beneficial nature of grain engineering for reduction of ion migration in perovskite solar cells.

Electronic structure of hybrid halide perovskite photovoltaic absorbers

Abstract: The performance of organometallic perovskite solar cells has rapidly surpassed those of both traditional dye-sensitized and organic photovoltaics, e.g. solar cells based on CH3NH3PbI3 have recently reached 18% conversion efficiency. We analyze its electronic structure and optical properties within the quasiparticle self-consistent GW approximation (QSGW ). Quasiparticle self-consistency is essential for an accurate description of the band structure: bandgaps are much larger than what is predicted by the local density approximation (LDA) or GW based on the LDA. Several characteristics combine to make the electronic structure of this material unusual. First, there is a strong driving force for ferroelectricity, as a consequence the polar organic moiety CH3NH3. The moiety is only weakly coupled to the PbI3 cage; thus it can rotate give rise to ferroelectric domains. This in turn will result in internal junctions that may aid separation of photoexcited electron and hole pairs, and may contribute to the current-voltage hysteresis found in perovskite solar cells. Second, spin orbit modifies both valence band and conduction band dispersions in a very unusual manner: both get split at the R point into two extrema nearby. This can be interpreted in terms of a large Dresselhaus term, which vanishes at R but for small excursions about R varies linearly in k. Conduction bands (Pb 6p character) and valence bands (I 5p) are affected differently; moreover the splittings vary with the orientation of the moiety. We will show how the splittings, and their dependence on the orientation of the moiety through the ferroelectric effect, have important consequences for both electronic transport and the optical properties of this material.

Mixed halide perovskites for spectrally stable and high-efficiency blue light-emitting diodes.

Abstract: Bright and efficient blue emission is key to further development of metal halide perovskite light-emitting diodes. Although modifying bromide/chloride composition is straightforward to achieve blue emission, practical implementation of this strategy has been challenging due to poor colour stability and severe photoluminescence quenching. Both detrimental effects become increasingly prominent in perovskites with the high chloride content needed to produce blue emission. Here, we solve these critical challenges in mixed halide perovskites and demonstrate spectrally stable blue perovskite light-emitting diodes over a wide range of emission wavelengths from 490 to 451 nanometres. The emission colour is directly tuned by modifying the halide composition. Particularly, our blue and deep-blue light-emitting diodes based on three-dimensional perovskites show high EQE values of 11.0% and 5.5% with emission peaks at 477 and 467 nm, respectively. These achievements are enabled by a vapour-assisted crystallization technique, which largely mitigates local compositional heterogeneity and ion migration. Achieving bright and efficient blue emission in metal halide perovskite light-emitting diodes has proven to be challenging. Here, the authors demonstrate high EQE and spectrally stable blue light-emitting diodes based on mixed halide perovskites, with emission from 490 to 451 nm by using a vapour-assisted crystallization technique.

Solid-state NMR spectroscopy

Abstract: Solid-state nuclear magnetic resonance (NMR) spectroscopy is an atomic-level method used to determine the chemical structure, three-dimensional structure, and dynamics of solids and semi-solids. This Primer summarizes the basic principles of NMR as applied to the wide range of solid systems. The fundamental nuclear spin interactions and the effects of magnetic fields and radiofrequency pulses on nuclear spins are the same as in liquid-state NMR. However, because of the anisotropy of the interactions in the solid state, the majority of high-resolution solid-state NMR spectra is measured under magic-angle spinning (MAS), which has profound effects on the types of radiofrequency pulse sequences required to extract structural and dynamical information. We describe the most common MAS NMR experiments and data analysis approaches for investigating biological macromolecules, organic materials, and inorganic solids. Continuing development of sensitivity-enhancement approaches, including 1H-detected fast MAS experiments, dynamic nuclear polarization, and experiments tailored to ultrahigh magnetic fields, is described. We highlight recent applications of solid-state NMR to biological and materials chemistry. The Primer ends with a discussion of current limitations of NMR to study solids, and points to future avenues of development to further enhance the capabilities of this sophisticated spectroscopy for new applications.

Revealing Charge Carrier Mobility and Defect Densities in Metal Halide Perovskites via Space-Charge-Limited Current Measurements

Abstract: Space-charge-limited current (SCLC) measurements have been widely used to study the charge carrier mobility and trap density in semiconductors. However, their applicability to metal halide perovskites is not straightforward, due to the mixed ionic and electronic nature of these materials. Here, we discuss the pitfalls of SCLC for perovskite semiconductors, and especially the effect of mobile ions. We show, using drift-diffusion (DD) simulations, that the ions strongly affect the measurement and that the usual analysis and interpretation of SCLC need to be refined. We highlight that the trap density and mobility cannot be directly quantified using classical methods. We discuss the advantages of pulsed SCLC for obtaining reliable data with minimal influence of the ionic motion. We then show that fitting the pulsed SCLC with DD modeling is a reliable method for extracting mobility, trap, and ion densities simultaneously. As a proof of concept, we obtain a trap density of 1.3 × 1013 cm-3, an ion density of 1.1 × 1013 cm-3, and a mobility of 13 cm2 V-1 s-1 for a MAPbBr3 single crystal.

Two birds with one stone: dual grain-boundary and interface passivation enables >22% efficient inverted methylammonium-free perovskite solar cells

Abstract: Advancing inverted (p–i–n) perovskite solar cells (PSCs) is key to further enhance the power conversion efficiency (PCE) and stability of flexible and perovskite-based tandem photovoltaics. Yet, the presence of defects at grain boundaries and in particular interfacial recombination at the perovskite/electron transporting layer interface induce severe non-radiative recombination losses, limiting the open-circuit voltage (VOC) and fill factor (FF) of PSCs in this architecture. In this work, we introduce a dual passivation strategy using the long chain alkylammonium salt phenethylammonium chloride (PEACl) both as an additive and for surface treatment to simultaneously passivate the grain boundaries and the perovskite/C60 interface. Using [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz) as a hole transporting layer and a methylammonium (MA)-free Cs0.18FA0.82PbI3 perovskite absorber with a bandgap of ∼1.57 eV, prolonged charge carrier lifetime and an on average 63 meV enhanced internal quasi-Fermi level splitting are achieved upon dual passivation compared to reference p–i–n PSCs. Thereby, we achieve one of the highest PCEs for p–i–n PSCs of 22.7% (stabilized at 22.3%) by advancing simultaneously the VOC and FF up to 1.162 V and 83.2%, respectively. Using a variety of experimental techniques, we attribute the positive effects to the formation of a heterogeneous 2D Ruddlesden–Popper (PEA)2(Cs1−xFAx)n−1Pbn(I1−yCly)3n+1 phase at the grain boundaries and surface of the perovskite films. At the same time, the activation energy for ion migration is significantly increased, resulting in enhanced stability of the PSCs under light, humidity, and thermal stress. The presented dual passivation strategy highlights the importance of defect management both in the grain boundaries and the surface of the perovskite absorber layer using a proper passivation material to achieve both highly efficient and stable inverted p–i–n PSCs.