Publications

Mixed-halide lead perovskites (MHLPs) are semiconductor materials with bandgaps that are tunable across the visible spectrum and have seen promising applications in photovoltaics and optoelectronics. However, their segregation into phases with enriched halide components, under resonant light illumination and/or electric field, have hindered their practical applications. Herein, we demonstrate the stabilization of the MHLP photoluminescence (PL) peak as a function of their excitation intensities. This effect is associated with the phase segregation of MHLPs and their subsequent remixing by photothermal heating. We conclude that the balance between these opposing processes dictates the equilibrium PL peak of the MHLPs. The findings in this work could serve as a potential approach to obtain MHLP with stable emission peaks under operating conditions.

Mixed-halide lead perovskites (MHPs) are promising materials for photovoltaics and optoelectronics due to their highly tunable band gaps. However, they phase segregate under continuous illumination or an electric field, the mechanism of which is still under debate. Herein we systematically measure the phase segregation behavior of polymer-encapsulated CH3NH3Pb(BrxI1-x)3 MHPs as a function of excitation intensity and the nominal halide ratio by in situ photoluminescence microspectroscopy and observe surprising phase dynamics at the beginning of the illumination. The initial phase segregation to I-rich and Br-rich phases is observed followed by the formation of a new mixed-halide phase within several seconds that has not been reported before. We propose that the photothermal effect is amplified at the small-size I-rich domains, which significantly changes the local phase segregation in the otherwise uniform film within milliseconds after illumination.

For a nanostructure sitting on top of an AlGaN:Er3+ thin film, a new thermal imaging technique is presented where dual cameras collect bandpass filtered videos from the H and S bands of Er3+ emission. We combine this thermal imaging technique with our newly developed time-resolved temperature measurement technique which relies on luminescence thermometry using Er3+ emission. This technique collects time-resolved traces from the H and S bands of Er3+ emission. The H and S signal traces are then used to reconstruct the time-resolved temperature transient when a nanostructure is illuminated with a pulsed 532 nm light. Two different types of samples are interrogated with these techniques (drop-casted gold nanosphere cluster and lithographically prepared gold nanodot) on the AlGaN:Er3+ film. Steady-state and time-resolved temperature data are collected when the samples are immersed in air and water. The results of time-resolved temperature-jump measurements from a cluster of gold nanospheres show extremely slow heat transfer when the cluster is immersed in water and nearly 200-fold increase when immersed in air. The low thermal diffusivity for the cluster in water suggests poor thermal contact between the cluster and the thermal bath. The lithographically prepared nanodot has much better adhesion to the AlGaN film, resulting in much higher thermal diffusivity in both air and water. This proof-of-concept demonstration opens a new way to measure the dynamics of the local heat generation and dissipation at the nanoparticle-media interface.

The ability to manipulate single protein molecules on a surface is useful for interfacing biology with many types of devices in optics, catalysis, bioengineering, and biosensing. Control of distance, orientation, and activity at the single molecule level will allow for the production of on-chip devices with increased biological activity. Cost effective methodologies for single molecule protein patterning with tunable pattern density and scalable coverage area remain a challenge. Herein, Hole Mask Colloidal Lithography is presented as a bench-top colloidal lithography technique that enables a glass coverslip to be patterned with functional streptavidin protein onto patches from 15-200 nm in diameter with variable pitch. Atomic force microscopy (AFM) was used to characterize the size of the patterned features on the glass surface. Additionally, single-molecule fluorescence microscopy was used to demonstrate the tunable pattern density, measure binding controls, and confirm patterned single molecules of functional streptavidin.

Reactive oxygen species (ROS) are a necessary evil in many biological systems and have been measured with fluorescent probes at the ensemble levels both in vitro and in vivo. Measuring ROS generated from a single molecule is important for mechanistic studies, yet measuring ROS near a dye-labeled single-molecule under illumination has been challenging. Here, we use CellROX, a group of ROS probes, to sense ROS near dye-stained DNA that has been flow-stretched and immobilized on a surface. ROS is responsible for the photodamage of DNA molecules under this circumstance. In this report, we confirmed the ROS sensing reaction in bulk solutions and optimized the conditions for single-molecule experiments including the selection of substrates, dye concentrations, probes in the CellROX series, excitation lasers, and emission filter-sets. We observed a correlation between ROS and the dye-labeled DNA and localized the ROS-activated CellROX probe molecules at both the ensemble level and the single-molecule level.

Patterning semiconducting materials are important for many applications such as microelectronics, displays, and photodetectors. Lead halide perovskites are an emerging class of semiconducting materials that can be patterned via solution-based methods. Here we report an all-benchtop patterning strategy by first generating a patterned surface with contrasting wettabilities to organic solvents that have been used in the perovskite precursor solution then spin-coating the solution onto the patterned surface. The precursor solution only stays in the area with higher affinity (wettability). We applied sequential sunlight-initiated thiol-ene reactions to functionalize (and pattern) both glass and conductive fluorine-doped tin oxide (FTO) transparent glass surfaces. The functionalized surfaces were measured with the solvent contact angles of water and different organic solvents and were further characterized by XPS, selective fluorescence staining, and selective DNA adsorption. By simply spin-coating and baking the perovskite precursor solution on the patterned substrates, we obtained perovskite thin-film microarrays. The spin-coated perovskite arrays were characterized by XRD, AFM, and SEM. We concluded that patterned substrate prepared via sequential sunlight-initiated thiol-ene click reactions is suitable to fabricate perovskite arrays via the benchtop process. In addition, the same patterned substrates can be reused several times until a favorable perovskite microarray is acquired. Among a few conditions we have tested, DMSO solvent and modified FTO surfaces with alternatively carboxylic acid and alkane is the best combination to obtain high-quality perovskite microarrays. The solvent contact angle of DMSO on carboxylic acid-modified FTO surface is nearly zero and 65±3° on octadecane modified FTO surface.

Thiol-ene click chemistry has become a powerful paradigm in synthesis, materials science, and surface modification in the past decade. In the photoinitiated thiol-ene reaction, an induction period is often observed before the major change in its kinetic curve, for which a possible mechanism is proposed in this report. Briefly, light soaking generates radicals following the zeroth-order reaction kinetics. The radical is the reactant that initializes the chain reaction of thiol-ene coupling, which is a first-order reaction. Combining both and under the light-limited conditions, a surprising kinetics represented by a Gaussian-like model evolves that is different from the exponential model used to describe the first-order reaction of the final product. The experimental data are fitted well with the new model, and the reaction kinetic constants can be pulled out from the fitting.

In this report, we observed that YOYO-1 immobilized on a glass surface is much brighter when dried (quantum yield 16±4% in the ambient air) or in hexane than in water (quantum yield  %).YOYO-1 is a typical cyanine dye that has a photo-isomerization reaction upon light illumination. In order to understand this quenching mechanism, we use femtosecond transient absorption spectroscopy to measure YOYO-1's electron dynamics after excitation directly. By deconvoluting the hot-ground-state absorption and the stimulated emission, the dynamics of electronic relaxation and balance are revealed. The results support the intermolecular charge transfer mechanism better than the intramolecular relaxation mechanism that has been widely believed before. We believe that the first step of the relaxation involves a Dexter charge transfer between the photo-excited YOYO-1 molecule and another guest molecule that is directly bound to the YOYO-1 giving two radicals with opposite signs of charges. The charges are recombined either directly between these two molecules, or both molecules start to rotate and separate from each other. Eventually, the two charges recombined non-radiatively via various pathways. These pathways are reflected on the complicated multi-exponential decay curves of YOYO-1 fluorescence lifetime measurements. This charge transfer mechanism suggests that (1) electrical insulation may help improve the quantum yield of YOYO-1 in polar solutions significantly and (2) a steric hindrance for the intramolecular rotation may have a less significant effect.

Super-resolution imaging of single DNA molecules via point accumulation for imaging in nanoscale topography (PAINT) has great potential to visualize fine DNA structures with nanometer resolution. In a typical PAINT video acquisition, dye molecules (YOYO-1) in solution sparsely bind to the target surfaces (DNA) whose locations can be mathematically determined by fitting their fluorescent point spread function. Many YOYO-1 molecules intercalate into DNA and remain there during imaging, and most of them have to be temporarily or permanently fluorescently bleached, often stochastically, to allow for the visualization of a few fluorescent events per DNA per frame of the video. Thus, controlling the fluorescence on-off rate is important in PAINT. In this paper, we study the photobleaching of YOYO-1 and its correlation with the quality of the PAINT images. At a low excitation laser power density, the photobleaching of YOYO-1 is too slow and a minimum required power density was identified, which can be theoretically predicted with the proposed method in this report.

The retention and elution of proteins in ion-exchange chromatography is routinely controlled by adjusting the mobile phase salt concentration. It has repeatedly been observed, as judged from adsorption isotherms, that the apparent heterogeneity of adsorption is lower at more-eluting, higher ionic strength. Here, we present an investigation into the mechanism of this phenomenon using a single-molecule, super-resolution imaging technique called motion-blur Points Accumulation for Imaging in Nanoscale Topography (mbPAINT). We observed that the number of functional adsorption sites was smaller at high ionic strength and that these sites had reduced desorption kinetic heterogeneity, and thus narrower predicted elution profiles, for the anion-exchange adsorption of α-lactalbumin on an agarose-supported, clustered-charge ligand stationary phase. Explanations for the narrowing of the functional population such as inter-protein interactions and protein or support structural changes were investigated through kinetic analysis, circular dichroism spectroscopy, and microscopy of agarose microbeads, respectively. The results suggest the reduction of heterogeneity is due to both electrostatic screening between the protein and ligand and tuning the steric availability within the agarose support. Overall, we have shown that single molecule spectroscopy can aid in understanding the influence of ionic strength on the population of functional adsorbent sites participating in the ion-exchange chromatographic separation of proteins.