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Compression and swelling of hydrogels in polymer solutions: A dominant-mode model
Get PDFThe swelling and compression of hydrogels in polymer solutions can be understood by considering hydrogel-osmolyte-solvent interactions which determine the osmotic pressure difference between the inside and the outside of a hydrogel particle and the changes in effective solvent quality for the hydrogel network. Using the theory of poroelasticity, we find the exact solution to hydrogel dynamics in a dilute polymer solution, which quantifies the effect of diffusion and partitioning of osmolyte and the related solvent quality change to the volumetric changes of the hydrogel network. By making a dominant mode assumption, we propose a new model for the swelling and compression dynamics of (spherical) hydrogels in concentrated polymer solutions. Osmolyte diffusion induces a bi-exponential response in the size of the hydrogel radius, whereas osmolyte partitioning and solvent quality effects induce mono-exponential responses. Comparison of the dominant-mode model to experiments provides reasonable values for the compressive bulk modulus of a hydrogel particle, the permeability of the hydrogel network and the diffusion constant of osmolyte molecules inside the hydrogel network. Our model shows that hydrogel-osmolyte interactions can be described in a conceptually simple manner, while still capturing the rich (de)swelling behaviors observed in experiments. We expect our approach to provide a roadmap for further research into and applications of hydrogel dynamics induced by, for example, changes in the temperature and the pH
Environmental Issues in the Structure and Ultrafast Kinetics of Acids and Hydrated Protons
Get PDFProtons (H+) are the most abundant cations in chemical processes. Proton itself is a superacid and in solution it always interacts either with the conjugate base or with the solvent molecules forming complex solvation structures. In this thesis we study the structure of hydrated protons in mixed solvents and in nanoconfined water. We also study the kinetics of proton transfer in bulk and nanoconfined water. The molecular events of proton transfer occur on picosecond time scale. Thus, to study structure and dynamics of various protonated species we use femtosecond pump-probe and two-dimensional infrared spectroscopy. In these methods we excite the vibrations of the solvated protons with an intense femtosecond pump pulse and measure the time dependent changes in the infrared absorption spectrum using a delayed weak probe pulse. From these spectral changes we can draw conclusions about the dynamics of energy redistribution within the proton solvation structures. In addition, from the dependence of the absorption change on the relative polarization of pump and probe pulses (parallel or perpendicular) we obtain the information about the relative orientation of the transition dipole moments of the vibrations and the molecular groups corresponding to them. This information helps us to determine geometry of molecular structures which participate in proton solvation and proton transfer
Understanding the Stability of MAPbBr3 versus MAPbI3: Suppression of Methylammonium Migration and Reduction of Halide Migration
Get PDFSolar 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
OrganoidTracker: Efficient cell tracking using machine learning and manual error correction
Get PDFTime-lapse microscopy is routinely used to follow cells within organoids, allowing direct study of division and differentiation patterns. There is an increasing interest in cell tracking in organoids, which makes it possible to study their growth and homeostasis at the single-cell level. As tracking these cells by hand is prohibitively time consuming, automation using a computer program is required. Unfortunately, organoids have a high cell density and fast cell movement, which makes automated cell tracking difficult. In this work, a semi-automated cell tracker has been developed. To detect the nuclei, we use a machine learning approach based on a convolutional neural network. To form cell trajectories, we link detections at different time points together using a min-cost flow solver. The tracker raises warnings for situations with likely errors. Rapid changes in nucleus volume and position are reported for manual review, as well as cases where nuclei divide, appear and disappear. When the warning system is adjusted such that virtually error-free lineage trees can be obtained, still less than 2% of all detected nuclei positions are marked for manual analysis. This provides an enormous speed boost over manual cell tracking, while still providing tracking data of the same quality as manual trackin
Close-Packed Ultrasmooth Self-assembled Monolayer of CsPbBr3 Perovskite Nanocubes
Get PDFThe use of colloidal self-assembly to form the complex multiscale patterns in many optoelectronic devices has been a long-standing dream of the nanoscience community. While great progress has been made using charged colloids in polar solvents, controlled assembly from nonpolar solvents is much more challenging. The major challenge is colloidal clustering caused by strong van der Waals (vdW) attraction between long-chain surface capping ligands passivating the surface of nanocrystals. Such clustering degrades ordering in packing during the self-assembly process. While ligand exchange to provide colloidal stability in polar phases is often an option, this is not the case for the exciting new class of halide perovskites due to the material’s solubility in essentially all polar solvents. Here, we report surface-functionalized self-assembly of luminescent CsPbBr3 perovskite nanocubes by partially replacing long-chain oleyl groups (18 carbon chain) with short-chain thiocyanate (SCN–). This enables the fabrication of ultrasmooth monolayer thin films of nanocubes with a root-mean-square (RMS) roughness of around 4 Å. This ultrasmooth large area self-assembled layer could act as high-efficiency optoelectronic devices like solar cells, light-emitting diodes (LEDs), transistors, etc. We correlate our experimental results with simulations, providing detailed predictions for lattice constants with chain conformations showing reduced free energy for cubes grafted with short-chain thiocyanate compared to long-chain oleyl groups, thus facilitating better self-assembly
Phase-Resolved Surface Plasmon Scattering Probed by Cathodoluminescence Holography
Get PDFHigh-energy (1–100 keV) electrons can coherently couple to plasmonic and dielectric nanostructures, creating cathodoluminescence (CL) of which the spectral features reveal details of the material’s resonant modes at a deep-subwavelength spatial resolution. While CL provides fundamental insight in optical modes, detecting its phase has remained elusive. Here, we use Fourier-transform CL holography to determine the far-field phase distribution of fields scattered from plasmonic nanoholes, nanocubes, and helical nanoapertures and reconstruct the angle-resolved phase distributions. From the derived fields, we derive the relative strength and phase of induced scattering dipoles. Fourier-transform CL holography opens up a new world of coherent light scattering and surface wave studies with nanoscale spatial resolution
Manganese Doping Stabilizes Perovskite Light-Emitting Diodes by Reducing Ion Migration
Get PDFLead-halide perovskite light-emitting diodes have recently emerged as high-performance devices. However, they degrade rapidly. This degradation has been attributed to the mixed ionic–electronic nature of these perovskites. Manganese doping increases the stability of perovskite light-emitting diodes, but the effects of manganese doping on ion migration are not well understood. We use impedance spectroscopy and transient ion-drift measurements to study the effect of manganese doping on ion migration in PEABr0.2Cs0.4MA0.6PbBr3 quasi-bulk two-/three-dimensional perovskite light-emitting diodes. We find that manganese doping enhances the activation energy for ion migration twofold and reduces the diffusion coefficient. These changes in the behavior of mobile ions help us to explain the improved stability in perovskite light-emitting diodes upon manganese doping and lead to a better understanding of the influence of passivating agents on ion migration and thus on the stability of the devices
The Application of Electron Backscatter Diffraction on Halide Perovskite Materials
Get PDFRecently, the application of electron backscatter diffraction (EBSD) in halide perovskites has enabled the correlation of the micro‐structural arrangement of polycrystalline grains with other properties (optical, electrical, mechanical, and chemical) in a “pixel‐by‐pixel” approach. Most studies so far have used an ultra‐sensitive electron beam detector that has sensitivity thousands of times higher than a traditional scintillator screen and charge coupled device camera, enabling much lower beam currents. An alternative approach has been the use of low vacuum measurement conditions to avoid charge buildup that leads to damage. This review focuses on introducing the classical EBSD technique to the halide perovskite community, where it has been highly underutilized due to beaminduced damage in these relatively unstable materials. Recent research is used to dispel some common misconceptions about grain boundaries in halide perovskites and highlight what has been learned by comparing and correlating EBSD with other techniques. Additionally, the remaining limitations, development challenges, and future of the EBSD technique for halide perovskites are discussed. Successful utilization of the EBSD technique as a common characterization tool in the halide perovskite community will enable scientists and engineers to develop maps of cross correlated properties, helping to unlock the full potential of this complex material system
Electron-Induced State Conversion in Diamond NV Centers Measured with Pump−Probe Cathodoluminescence Spectroscopy
Get PDFNitrogen-vacancy (NV) centers in diamond have been exploited as reliable single-photon emitters, with applications in quantum technologies and metrology. Two charge states are known for NV centers: NV0 and NV–, with the latter being mostly studied due to its long electron spin coherence time. Therefore, control over the charge state of the NV centers is essential. However, the understanding of the dynamics between the different states still remains challenging. Here we show that electron excitation induces the conversion from NV– to NV0 through electron-induced carrier generation. We present for the first time ultrafast pump-probe cathodoluminescence spectroscopy, with electron pulses as pump, and laser pulses as probe, to prepare and read out the NV states. The experimental data is explained with a model considering carrier dynamics (0.8 ns), NV0 spontaneous emission (20 ns) and NV0NV– back transfer (500 ms). Our results provide new insights into the NV–NV0 conversion dynamics, and into the use of pump-probe cathodoluminescence as a nanoscale NV characterization tool.Nitrogen-vacancy (NV) centers in diamond are reliable single-photon emitters, with applications in quantum technologies and metrology. Two charge states are known for NV centers, NV0 and NV–, with the latter being mostly studied due to its long electron spin coherence time. Therefore, control over the charge state of the NV centers is essential. However, an understanding of the dynamics between the different states still remains challenging. Here, conversion from NV– to NV0 due to electron-induced carrier generation is shown. Ultrafast pump–probe cathodoluminescence spectroscopy is presented for the first time, with electron pulses as pump and laser pulses as probe, to prepare and read out the NV states. The experimental data are explained with a model considering carrier dynamics (0.8 ns), NV0 spontaneous emission (20 ns), and NV0 → NV– back transfer (500 ms). The results provide new insights into the NV– → NV0 conversion dynamics and into the use of pump–probe cathodoluminescence as a nanoscale NV characterization tool
Polaritonic molecular clock for all-optical ultrafast imaging of wavepacket dynamics without probe pulses
Get PDFConventional approaches to probing ultrafast molecular dynamics rely on the use of synchronized laser pulses with a well-defined time delay. Typically, a pump pulse excites a molecular wavepacket. A subsequent probe pulse can then dissociate or ionize the molecule, and measurement of the molecular fragments provides information about where the wavepacket was for each time delay. Here, we propose to exploit the ultrafast nuclear-position-dependent emission obtained due to large light–matter coupling in plasmonic nanocavities to image wavepacket dynamics using only a single pump pulse. We show that the time-resolved emission from the cavity provides information about when the wavepacket passes a given region in nuclear configuration space. This approach can image both cavity-modified dynamics on polaritonic (hybrid light–matter) potentials in the strong light–matter coupling regime and bare-molecule dynamics in the intermediate coupling regime of large Purcell enhancements, and provides a route towards ultrafast molecular spectroscopy with plasmonic nanocavities