Elke Debroye

Degradation of Methylammonium Lead Iodide Perovskite Structures through Light and Electron Beam Driven Ion Migration

Organometal halide perovskites show promising features for cost-effective application in photovoltaics. The material instability remains a major obstacle to broad application because of the poorly understood degradation pathways. Here, we apply simultaneous luminescence and electron microscopy on perovskites for the first time, allowing us to monitor in situ morphology evolution and optical properties upon perovskite degradation. Interestingly, morphology, photoluminescence (PL), and cathodoluminescence of perovskite samples evolve differently upon degradation driven by electron beam (e-beam) or by light. A transversal electric current generated by a scanning electron beam leads to dramatic changes in PL and tunes the energy band gaps continuously alongside film thinning. In contrast, light-induced degradation results in material decomposition to scattered particles and shows little PL spectral shifts. The differences in degradation can be ascribed to different electric currents that drive ion migration. Moreover, solution-processed perovskite cuboids show heterogeneity in stability which is likely related to crystallinity and morphology. Our results reveal the essential role of ion migration in perovskite degradation and provide potential avenues to rationally enhance the stability of perovskite materials by reducing ion migration while improving morphology and crystallinity. It is worth noting that even moderate e-beam currents (86 pA) and acceleration voltages (10 kV) readily induce significant perovskite degradation and alter their optical properties. Therefore, attention has to be paid while characterizing such materials using scanning electron microscopy or transmission electron microscopy techniques.

Photoluminescence Blinking of Single-Crystal Methylammonium Lead Iodide Perovskite Nanorods Induced by Surface Traps

Photoluminescence (PL) of organometal halide perovskite materials reflects the charge dynamics inside of the material and thus contains important information for understanding the electro-optical properties of the material. Interpretation of PL blinking of methylammonium lead iodide (MAPbI3) nanostructures observed on polycrystalline samples remains puzzling owing to their intrinsic disordered nature. Here, we report a novel method for the synthesis of high-quality single-crystal MAPbI3 nanorods and demonstrate a single-crystal study on MAPbI3 PL blinking. At low excitation power densities, two-state blinking was found on individual nanorods with dimensions of several hundred nanometers. A super-resolution localization study on the blinking of individual nanorods showed that single crystals of several hundred nanometers emit and blink as a whole, without showing changes in the localization center over the crystal. Moreover, both the blinking ON and OFF times showed power-law distributions, indicating trapping–detrapping processes. This is further supported by the PL decay times of the individual nanorods, which were found to correlate with the ON/OFF states. Furthermore, a strong environmental dependence of the nanorod PL blinking was revealed by comparing the measurements in vacuum, nitrogen, and air, implying that traps locate close to crystal surfaces. We explain our observations by proposing surface charge traps that are likely related to under-coordinated lead ions and methylammonium vacancies to result in the PL blinking observed here.

Controlled Synthesis of a Novel Heteropolymetallic Complex with Selectively Incorporated Lanthanide(III) Ions

A novel synthetic strategy toward a heteropolymetallic lanthanide complex with selectively incorporated gadolinium and europium ions is outlined. Luminescence and relaxometric measurements suggest possible applications in bimodal (magnetic resonance/optical) imaging.

Dysprosium Complexes and Their Micelles as Potential Bimodal Agents for Magnetic Resonance and Optical Imaging

Six diethylene triamine pentaacetic acid (DTPA) bisamide derivatives functionalized with p-toluidine (DTPA-BTolA), 6-aminocoumarin (DTPA-BCoumA), 1-naphthalene methylamine (DTPA-BNaphA), 4-ethynylaniline (DTPA-BEthA), p-dodecylaniline (DTPA-BC12PheA) and p-tetradecyl-aniline (DTPA-BC14PheA) were coordinated to dysprosium(III) and the magnetic and optical properties of the complexes were examined in detail. The complexes consisting of amphiphilic ligands (DTPA-BC12PheA and DTPA-BC14PheA) were further assembled into mixed micelles. Upon excitation into the ligand levels, the complexes display characteristic Dy(III) emission with quantum yields of 0.3-0.5% despite the presence of one water molecule in the first coordination sphere. A deeper insight into the energy-transfer processes has been obtained by studying the photophysical properties of the corresponding Gd(III) complexes. Since the luminescence quenching effect is decreased by the intervention of non-ionic surfactant, quantum yields up to 1% are obtained for the micelles. The transverse relaxivity r2 per Dy(III) ion at 500 MHz and 310 K reaches a maximum value of 27.4 s(-1) mM(-1) for Dy-DTPA-BEthA and 36.0 s(-1) mM(-1) for the Dy-DTPA-BC12PheA assemblies compared with a value of 0.8 s(-1) mM(-1) for Dy-DTPA. The efficient T2 relaxation, especially at high magnetic field strengths, is sustained by the high magnetic moment of the dysprosium ion, the coordination of water molecules with slow water exchange kinetics and long rotational correlation times. These findings open the way to the further development of bimodal optical and magnetic resonance imaging probes starting from single lanthanide compounds.

Facet-Dependent Photoreduction on Single ZnO Crystals

Photocatalytic reactions occur at the crystal–solution interface, and hence specific crystal facet expression and surface defects can play an important role. Here we investigate the structure-related photoreduction at zinc oxide (ZnO) microparticles via integrated light and electron microscopy in combination with silver metal photodeposition. This enables a direct visualization of the photoreduction activity at specific crystallographic features. It is found that silver nanoparticle photodeposition on dumbbell-shaped crystals mainly takes place at the edges of O-terminated (0001̅) polar facets. In contrast, on ZnO microrods photodeposition is more homogeneously distributed with an increased activity at {101̅1̅} facets. Additional time-resolved measurements reveal a direct spatial link between the enhanced photoactivity and increased charge carrier lifetimes. These findings contradict previous observations based on indirect, bulk-scale experiments, assigning the highest photocatalytic activity to polar facets. The presented research demonstrates the need for advanced microscopy techniques to directly probe the location of photocatalytic activity.

Rationalizing Acid Zeolite Performance on the Nanoscale by Correlative Fluorescence and Electron Microscopy

The performance of zeolites as solid acid catalysts is strongly influenced by the accessibility of active sites. However, synthetic zeolites typically grow as complex aggregates of small nanocrystallites rather than perfect single crystals. The structural complexity must therefore play a decisive role in zeolite catalyst applicability. Traditional tools for the characterization of heterogeneous catalysts are unable to directly relate nanometer-scale structural properties to the corresponding catalytic performance. In this work, an innovative correlative super-resolution fluorescence and scanning electron microscope is applied, and the appropriate analysis procedures are developed to investigate the effect of small-port H-mordenite (H-MOR) morphology on the catalytic performance, along with the effects of extensive acid leaching. These correlative measurements revealed catalytic activity at the interface between intergrown H-MOR crystallites that was assumed inaccessible, without compromising the shape selective properties. Furthermore, it was found that extensive acid leaching led to an etching of the originally accessible microporous structure, rather than the formation of an extended mesoporous structure. The associated transition of small-port to large-port H-MOR therefore did not render the full catalyst particle functional for catalysis. The applied characterization technique allows a straightforward investigation of the zeolite structure–activity relationship beyond the single-particle level. We conclude that such information will ultimately lead to an accurate understanding of the relationship between the bulk scale catalyst behavior and the nanoscale structural features, enabling a rationalization of catalyst design.

Facile Morphology-Controlled Synthesis of Organolead Iodide Perovskite Nanocrystals Using Binary Capping Agents

Abstract Controlling the morphology of organolead halide perovskite crystals is crucial to a fundamental understanding of the materials and to tune their properties for device applications. Here, we report a facile solution‐based method for morphology‐controlled synthesis of rod‐like and plate‐like organolead halide perovskite nanocrystals using binary capping agents. The morphology control is likely due to an interplay between surface binding kinetics of the two capping agents at different crystal facets. By high‐resolution scanning transmission electron microscopy, we show that the obtained nanocrystals are monocrystalline. Moreover, long photoluminescence decay times of the nanocrystals indicate long charge diffusion lengths and low trap/defect densities. Our results pave the way for large‐scale solution synthesis of organolead halide perovskite nanocrystals with controlled morphology for future device applications.

Effect of the substitution position (2, 3 or 8) on the spectroscopic and photophysical properties of BODIPY dyes with a phenyl, styryl or phenylethynyl group

A very active branch of organic chemistry is putting great effort into tailoring fluorescent dyes for a myriad of applications, from technological to bioanalytical and biomedical applications. Among the major families of fluorophores, those derived from 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY dyes) are undergoing a recent boost thanks to the simplicity and robustness of the chemistry involved. The BODIPY core can be modified with numerous side groups, the 8-position being a modification place with important effects on the spectroscopic and photophysical properties of the resulting dyes. Likewise, previous work has shown that the addition of groups attached at the 3- and 2-positions can result in dyes with very different properties. Herein, we generalize the effect of the substituent side groups by studying nine BODIPY dyes substituted with a phenyl, styryl or phenylethynyl moiety at the 2-, 3- or 8-position of the BODIPY scaffold. Within the class of phenyl- or phenylethynyl-substituted dyes, substitution at the 2-position always leads to dyes with the broadest bandwidths and the largest Stokes shifts. We investigate the solvent effect on the spectroscopic properties of the dyes, using four empirical solvent scales (dipolarity, polarizability, acidity and basicity: Catalan, J. Phys. Chem., 2009, 113, 5951). These analyses identify solvent dipolarity and polarizability as critical parameters accounting for the observed solvent-dependent shifts of the absorption and emission maxima. Finally, time-dependent density functional theory calculations provide insights into the structural and energetic issues concerning the spectroscopic properties of these fluorophores.

Following the stability of amphiphilic nanoaggregates by using intermolecular energy transfer

An intermolecular energy transfer system is developed for studying the stability of nanoaggregate(s) (NAs) in complex solution and cell culture by one- and two-photon fluorescence microscopy and optical imaging. The system allows facile addition of one or more tumor targeting molecules, one of which is exemplified here. NAs functionalized with an MRI and optical probe, with and without folic acid, remain stable in fetal bovine serum for at least 4 hours. HeLa cell cultures showed a clear difference between NAs non-targeted and targeted to folate receptors, with both NAs appearing to be taken up by the cells through different mechanisms. An MRI relaxivity, r1, of 9 mM-1 s-1 at 310 K and 1.4 T was measured associated with the increased rotational correlation time of the NAs. These NAs may have application in the targeted drug delivery of hydrophobic drugs such as doxorubicin (DOX).

The power of single molecule microscopy: from nanoparticle investigations to microbiome analysis

Optical microscopy has been a tool of choice ever since van Leeuwenhoek used Hookes microscope to observe biological specimens. Chief among its advantages is the fact that imaging is noninvasive. In combination with the straightforward sample preparation and general convenience, optical microscopes remain essential to many aspects of modern-day research.