Single-Particle Analysis of the Photodegradation of Submicron Polystyrene Particles Using Infrared Photothermal Heterodyne Imaging.

Sunlight irradiation is the predominant process for degrading plastics in the environment, but our current understanding of the degradation of smaller, submicron (<1000 nm) particles is limited due to prior analytical constraints. We used infrared photothermal heterodyne imaging (IR-PHI) to simultaneously analyze the chemical and morphological changes of single polystyrene (PS) particles (∼1000 nm) when exposed to ultraviolet (UV) irradiation (λ = 250-400 nm). Within 6 h of irradiation, infrared bands associated with the backbone of PS decreased, accompanied by a reduction in the particle size. Concurrently, the formation of several spectral features due to photooxidation was attributed to ketones, carboxylic acids, aldehydes, esters, and lactones. Spectral outcomes were used to present an updated reaction scheme for the photodegradation of PS. After 36 h, the average particle size was reduced to 478 ± 158 nm. The rates of size decrease and carbonyl band area increase were -24 ± 3.0 nm h-1 and 2.1 ± 0.6 cm-1 h-1, respectively. Using the size-related rate, we estimated that under peak terrestrial sunlight conditions, it would take less than 500 h for a 1000 nm PS particle to degrade to 1 nm.

Mixed Ligand Passivation as the Origin of Near-Unity Emission Quantum Yields in CsPbBr3 Nanocrystals.

Key features of syntheses, involving the quaternary ammonium passivation of CsPbBr3 nanocrystals (NCs), include stable, reproducible, and large (often near-unity) emission quantum yields (QYs). The archetypical example involves didodecyl dimethyl ammonium (DDDMA+)-passivated CsPbBr3 NCs where robust QYs stem from interactions between DDDMA+ and NC surfaces. Despite widespread adoption of this synthesis, specific ligand-NC surface interactions responsible for large DDDMA+-passivated NC QYs have not been fully established. Multidimensional nuclear magnetic resonance experiments now reveal a new DDDMA+-NC surface interaction, beyond established "tightly bound" DDDMA+ interactions, which strongly affects observed emission QYs. Depending upon the existence of this new DDDMA+ coordination, NC QYs vary broadly between 60 and 85%. More importantly, these measurements reveal surface passivation through unexpected didodecyl ammonium (DDA+) that works in concert with DDDMA+ to produce near-unity (i.e., >90%) QYs.

Far-field midinfrared superresolution imaging and spectroscopy of single high aspect ratio gold nanowires.

Limited approaches exist for imaging and recording spectra of individual nanostructures in the midinfrared region. Here we use infrared photothermal heterodyne imaging (IR-PHI) to interrogate single, high aspect ratio Au nanowires (NWs). Spectra recorded between 2,800 and 4,000 cm-1 for 2.5-3.9-µm-long NWs reveal a series of resonances due to the Fabry-Pérot modes of the NWs. Crucially, IR-PHI images show structure that reflects the spatial distribution of the NW absorption, and allow the resonances to be assigned to the m = 3 and m = 4 Fabry-Pérot modes. This far-field optical measurement has been used to image the mode structure of plasmon resonances in metal nanostructures, and is made possible by the superresolution capabilities of IR-PHI. The linewidths in the NW spectra range from 35 to 75 meV and, in several cases, are significantly below the limiting values predicted by the bulk Au Drude damping parameter. These linewidths imply long dephasing times, and are attributed to reduction in both radiation damping and resistive heating effects in the NWs. Compared to previous imaging studies of NW Fabry-Pérot modes using electron microscopy or near-field optical scanning techniques, IR-PHI experiments are performed under ambient conditions, enabling detailed studies of how the environment affects mid-IR plasmons.

Single-molecule characterization of a bright and photostable deep-red fluorescent squaraine-figure-eight (SF8) dye.

Squaraine Figure Eight (SF8) dyes are a unique class of deep-red fluorescent dyes with self-threaded molecular architecture that provides structural rigidity while simultaneously encapsulating and protecting the emissive fluorochrome. Previous cell microscopy and bulk phase studies of SF8 dyes indicated order of magnitude enhancements in photostability over conventional pentamethine cyanine dyes such as Cy5. Studies conducted at the single molecule level now reveal that these ensemble level enhancements carry over to the single molecule level in terms of enhanced emission quantum yields, longer times to photobleaching, and enhanced total photon yields. When compared to Cy5, the SF8-based dye SF8(D4)2 possesses a three-fold larger single molecule emission quantum yield, exhibits order of magnitude longer average times before photobleaching, and exhibits twenty times larger photon yields. Additional features such as water solubility, fluorochrome encapsulation to protect it against nucleophilic attack, and selective biomarker targeting capability make SF8-based dyes promising candidates for biological labeling and microscopy applications and single molecule tracking.

Halide Ion Migration in Perovskite Nanocrystals and Nanostructures.

ConspectusThe optical and electronic properties of metal halide perovskites provide insight into the operation of solar cells as well as their long-term operational stability. Halide mobility in perovskite films is an important factor influencing solar cell performance. One can visualize halide ion migration through halide exchange between two nanocrystal suspensions or between physically paired films of two different metal halide perovskites. The ability to tune band gap by varying halide ratios (Cl:Br or Br:I) allows the synthesis of mixed halide perovskites with tailored absorption and emission across the entire visible spectrum. Interestingly, mixed halide (e.g., MAPb(Br0.5I0.5)3) films undergo phase segregation to form Br-rich and I-rich sites under steady state illumination. Upon halting illumination, segregated phases mix to restore original mixed halide compositions. Introducing multiple cations (Cs, formamidinium) at the A site or alloying with Cl greatly suppresses halide mobilities. Long-term irradiation of MAPb(Br0.5I0.5)3 films also cause expulsion of iodide leaving behind Br-rich phases. Hole trapping at I-rich sites in MAPb(Br0.5I0.5)3 is considered to be an important step in inducing halide mobility in photoirradiated films. This Account focuses on halide ion migration in nanocrystals and nanostructured films driven by entropy of mixing in dark and phase segregation under light irradiation.

Using Infrared Photothermal Heterodyne Imaging to Characterize Micro- and Nanoplastics in Complex Environmental Matrices.

A key challenge for addressing micro- and nanoplastics (MNPs) in the environment is being able to characterize their chemical properties, morphologies, and quantities in complex matrices. Current techniques, such as Fourier transform infrared spectroscopy, provide these broad characterizations but are unsuitable for studying MNPs in spectrally congested or complex chemical environments. Here, we introduce a new, super-resolution infrared absorption technique to characterize MNPs, called infrared photothermal heterodyne imaging (IR-PHI). IR-PHI has a spatial resolution of ∼300 nm and can determine the chemical identity, morphology, and quantity of MNPs in a single analysis with high sensitivity. Specimens are supported on CaF2 coverslips under ambient conditions from where we (1) quantify MNPs from nylon tea bags after steeping in ultrapure water at 25 and 95 °C, (2) identify MNP chemical or morphological changes after steeping at 95 °C, and (3) chemically identify MNPs in sieved road dust. In all cases, no special sample preparation was required. MNPs released from nylon tea bags at 25 °C were fiber-like and had characteristic IR frequencies corresponding to thermally extruded nylon. At 95 °C, degradation of the nylon chemical structure was observed via the disappearance of amide group IR frequencies, indicating chain scission of the nylon backbone. This degradation was also observed through morphological changes, where MNPs altered shape from fiber-like to quasi-spherical. In road dust, IR-PHI analysis reveals the presence of numerous aggregate and single-particle (<3 µm) MNPs composed of rubber and nylon.

Deep image restoration for infrared photothermal heterodyne imaging.

Infrared photothermal heterodyne imaging (IR-PHI) is an all-optical table top approach that enables super-resolution mid-infrared microscopy and spectroscopy. The underlying principle behind IR-PHI is the detection of photothermal changes to specimens induced by their absorption of infrared radiation. Because detection of resulting refractive index and scattering cross section changes is done using a visible (probe) laser, IR-PHI exhibits a spatial resolution of ∼300 nm. This is significantly below the mid-infrared diffraction limit and is unlike conventional infrared absorption microscopy where spatial resolution is of order ∼5µm. Despite having achieved mid-infrared super-resolution, IR-PHI's spatial resolution is ultimately limited by the visible probe laser's diffraction limit. This hinders immediate application to studying samples residing in spatially congested environments. To circumvent this, we demonstrate further enhancements to IR-PHI's spatial resolution using a deep learning network that addresses the Abbe diffraction limit as well as background artifacts, introduced by experimental raster scanning. What results is a twofold improvement in feature resolution from 300 to ∼150 nm.

Thermal Decoherence of Superradiance in Lead Halide Perovskite Nanocrystal Superlattices.

Recent experiments by Rainò et al. ( Nature 2018, 563, 671-675) have documented cooperative emission from CsPbBr3 nanocrystal superlattices, exhibiting the hallmarks of low-temperature superradiance. In particular, the optical response is coherent and the radiative decay rate is increased by a factor of 3, relative to that of individual nanocrystals. However, the increase is 6 orders of magnitude smaller than what is theoretically expected from the superradiance of large assemblies, consisting of 106-108 interacting nanocrystals. Here, we develop a theoretical model of superradiance for such systems and show that thermal decoherence is largely responsible for the drastic reduction of the radiative decay rate in nanocrystal superlattices. Our theoretical approach explains the experimental results ( Nature 2018, 563, 671-675), provides insight into the design of small nanocrystal superlattices, and shows a 4 orders of magnitude enhancement in superradiant response. These quantitative predictions pave the path toward observing superradiance at higher temperatures.

Approaches to mid-infrared, super-resolution imaging and spectroscopy.

This perspective highlights recent advances in super-resolution, mid-infrared imaging and spectroscopy. It provides an overview of the different near field microscopy techniques developed to address the problem of chemically imaging specimens in the mid-infrared "fingerprint" region of the spectrum with high spatial resolution. We focus on a recently developed far-field optical technique, called infrared photothermal heterodyne imaging (IR-PHI), and discusses the technique in detail. Its practical implementation in terms of equipment used, optical geometries employed, and underlying contrast mechanism are described. Milestones where IR-PHI has led to notable advances in bioscience and materials science are summarized. The perspective concludes with a future outlook for robust and readily accessible high spatial resolution, mid-infrared imaging and spectroscopy techniques.

Crystal Structure of Individual CsPbBr3 Perovskite Nanocubes.

The atomic structure of CsPbBr3 nanocubes (NCs) was studied at the single-particle level via a high-resolution transmission electron microscopy (HRTEM) defocus-series analysis. The technique entails acquiring lattice-resolved HRTEM images of individual NCs over progressive defocus values. CsPbBr3 NC atomic structure was evaluated by comparing acquired experimental data to simulated lattice-resolved images and corresponding Fourier transform patterns of both orthorhombic ( Pnma) and cubic ( Pm3̅m) CsPbBr3 polymorphs. Herein, CsPbBr3 NCs with average edge lengths ( l) of l ∼ 10 and 5 nm are analyzed using the aforementioned technique. In the former, we find evidence for the coexistence of both cubic and orthorhombic lattices. In the latter, solely cubic character is observed, illustrating a potential size dependency to the crystal symmetry of CsPbBr3 NCs. Such structural measurements provide critical insight into elucidating the structure/(optical and electrical) function relationship of CsPbBr3 NCs.

Molybdenum Carbamate Nanosheets as a New Class of Potential Phase Change Materials.

We report for the first time the synthesis of large, free-standing, Mo2O2(µ-S)2(Et2dtc)2 (MoDTC) nanosheets (NSs), which exhibit an electron-beam induced crystalline-to-amorphous phase transition. Both electron beam ionization and femtosecond (fs) optical excitation induce the phase transition, which is size-, morphology-, and composition-preserving. Resulting NSs are the largest, free-standing regularly shaped two-dimensional amorphous nanostructures made to date. More importantly, amorphization is accompanied by dramatic changes to the NS electrical and optical response wherein resulting amorphous species exhibit room-temperature conductivities 5 orders of magnitude larger than those of their crystalline counterparts. This enhancement likely stems from the amorphization-induced formation of sulfur vacancy-related defects and is supported by temperature-dependent transport measurements, which reveal efficient variable range hopping. MoDTC NSs represent one instance of a broader class of transition metal carbamates likely having applications because of their intriguing electrical properties as well as demonstrated ability to toggle metal oxidation states.

Origin of the Size-Dependent Stokes Shift in CsPbBr3 Perovskite Nanocrystals.

The origin of the size-dependent Stokes shift in CsPbBr3 nanocrystals (NCs) is explained for the first time. Stokes shifts range from 82 to 20 meV for NCs with effective edge lengths varying from ∼4 to 13 nm. We show that the Stokes shift is intrinsic to the NC electronic structure and does not arise from extrinsic effects such as residual ensemble size distributions, impurities, or solvent-related effects. The origin of the Stokes shift is elucidated via first-principles calculations. Corresponding theoretical modeling of the CsPbBr3 NC density of states and band structure reveals the existence of an intrinsic confined hole state 260 to 70 meV above the valence band edge state for NCs with edge lengths from ∼2 to 5 nm. A size-dependent Stokes shift is therefore predicted and is in quantitative agreement with the experimental data. Comparison between bulk and NC calculations shows that the confined hole state is exclusive to NCs. At a broader level, the distinction between absorbing and emitting states in CsPbBr3 is likely a general feature of other halide perovskite NCs and can be tuned via NC size to enhance applications involving these materials.

Heterogeneous Fluorescence Intermittency in Single Layer Reduced Graphene Oxide.

We provide, for the first time, direct experimental evidence for heterogeneous blinking in reduced graphene oxide (rGO) during photolysis. The spatially resolved intermittency originates from regions within individual rGO sheets and shows 1/f-like power spectral density. We describe the evolution of rGO blinking using the multiple recombination center (MRC) model that captures common features of nanoscale blinking. Our results illustrate the universal nature of blinking and suggest a common microscopic origin for the effect.

Direct observation of single layer graphene oxide reduction through spatially resolved, single sheet absorption/emission microscopy.

Laser reduction of graphene oxide (GO) offers unique opportunities for the rapid, nonchemical production of graphene. By tuning relevant reduction parameters, the band gap and conductivity of reduced GO can be precisely controlled. In situ monitoring of single layer GO reduction is therefore essential. In this report, we show the direct observation of laser-induced, single layer GO reduction through correlated changes to its absorption and emission. Absorption/emission movies illustrate the initial stages of single layer GO reduction, its transition to reduced-GO (rGO) as well as its subsequent decomposition upon prolonged laser illumination. These studies reveal GO's photoreduction life cycle and through it native GO/rGO absorption coefficients, their intrasheet distributions as well as their spatial heterogeneities. Extracted absorption coefficients for unreduced GO are α405 nm ≈ 6.5 ± 1.1 × 10(4) cm(-1), α520 nm ≈ 2.1 ± 0.4 × 10(4) cm(-1), and α640 nm ≈ 1.1 ± 0.3 × 10(4) cm(-1) while corresponding rGO α-values are α405 nm ≈ 21.6 ± 0.6 × 10(4) cm(-1), α520 nm ≈ 16.9 ± 0.4 × 10(4) cm(-1), and α640 nm ≈ 14.5 ± 0.4 × 10(4) cm(-1). More importantly, the correlated absorption/emission imaging provides us with unprecedented insight into GO's underlying photoreduction mechanism, given our ability to spatially resolve its kinetics and to connect local rate constants to activation energies. On a broader level, the developed absorption imaging is general and can be applied toward investigating the optical properties of other two-dimensional materials, especially those that are nonemissive and are invisible to current single molecule optical techniques.

Direct observation of spatially heterogeneous single-layer graphene oxide reduction kinetics.

Graphene oxide (GO) is an important precursor in the production of chemically derived graphene. During reduction, GO's electrical conductivity and band gap change gradually. Doping and chemical functionalization are also possible, illustrating GO's immense potential in creating functional devices through control of its local hybridization. Here we show that laser-induced photolysis controllably reduces individual single-layer GO sheets. The reaction can be followed in real time through sizable decreases in GO's photoluminescence efficiency along with spectral blueshifts. As-produced reduced graphene oxide (rGO) sheets undergo additional photolysis, characterized by dramatic emission enhancements and spectral redshifts. Both GO's reduction and subsequent conversion to photobrightened rGO are captured through movies of their photoluminescence kinetics. Rate maps illustrate sizable spatial and temporal heterogeneities in sp(2) domain growth and reveal how reduction "flows" across GO and rGO sheets. The observed heterogeneous reduction kinetics provides mechanistic insight into GO's conversion to chemically derived graphene and highlights opportunities for overcoming its dynamic, chemical disorder.

Resonant Multiple-Phonon Absorption Causes Efficient Anti-Stokes Photoluminescence in CsPbBr3 Nanocrystals.

Lead halide perovskite nanocrystals, such as CsPbBr3, exhibit efficient photoluminescence (PL) up-conversion, also referred to as anti-Stokes photoluminescence (ASPL). This is a phenomenon where irradiating nanocrystals up to 100 meV below gap results in higher energy band edge emission. Most surprising is that ASPL efficiencies approach unity and involve single-photon interactions with multiple phonons. This is unexpected given the statistically disfavored nature of multiple-phonon absorption. Here, we report and rationalize near-unity anti-Stokes photoluminescence efficiencies in CsPbBr3 nanocrystals and attribute them to resonant multiple-phonon absorption by polarons. The theory explains paradoxically large efficiencies for intrinsically disfavored, multiple-phonon-assisted ASPL in nanocrystals. Moreover, the developed microscopic mechanism has immediate and important implications for applications of ASPL toward condensed phase optical refrigeration.

Modeling the Photoelectrochemical Evolution of Lead-Based, Mixed-Halide Perovskites Due to Photosegregation.

Lead-based, mixed-halide perovskites such as methylammonium lead iodide-bromide [MAPb(I1-xBrx)3] undergo anion photosegregation under illumination. This is observed as low-band-gap photoluminescence from photogenerated iodine-rich domains due to favorable band offsets that induce carrier funneling into them. Unfortunately, theoretical rationalizations of mixed-halide photosegregation are complicated by biases inherent in photoluminescence-based observations. Recent compositionally weighted X-ray diffraction (XRD) measurements now reveal broad distributions of photosegregated stoichiometries not captured by existing photosegregation models. To better bridge experiment and theory, we perform kinetic Monte Carlo (KMC) simulations of photosegregation within the context of a band-gap-based thermodynamic model, which has previously accounted for numerous experimental observations. Our KMC simulations are modified to consider high carrier density Fermi-Dirac statistics that result from carrier funneling and accumulation within photosegregated I-rich domains. Obtained KMC results reproduce broad terminal halide (xterminal) distributions seen experimentally and illustrate how they are characterized by a central, heavily I-enriched stoichiometry. I-rich domain "drifting" during photosegregation rationalizes the long photosegregation time scales seen experimentally with drifting simultaneously, producing a wake of variable stoichiometry I-rich inclusions that form the lion's share of stoichiometric heterogeneities seen in compositionally weighted XRD measurements. These simulations and accompanying rationalizations further reveal a general criterion for realizing favorable free energies to induce demixing. Central to the criterion is the statistical occupation of low gap inclusions in the parent alloy by excitations. The resulting model thus provides a general framework for conceptualizing mixed-halide perovskite light and temperature sensitivities mediated by photocarriers.

Right Prefrontal Cortical Thickness Is Associated With Response to Cognitive-Behavioral Therapy in Children With Obsessive-Compulsive Disorder.

OBJECTIVE: Cognitive-behavioral therapy (CBT) is considered a first-line treatment for obsessive-compulsive disorder (OCD) in pediatric and adult populations. Nevertheless, some patients show partial or null response. The identification of predictors of CBT response may improve clinical management of patients with OCD. Here, we aimed to identify structural magnetic resonance imaging (MRI) predictors of CBT response in 2 large series of children and adults with OCD from the worldwide ENIGMA-OCD consortium. METHOD: Data from 16 datasets from 13 international sites were included in the study. We assessed which variations in baseline cortical thickness, cortical surface area, and subcortical volume predicted response to CBT (percentage of baseline to post-treatment symptom reduction) in 2 samples totaling 168 children and adolescents (age range 5-17.5 years) and 318 adult patients (age range 18-63 years) with OCD. Mixed linear models with random intercept were used to account for potential cross-site differences in imaging values. RESULTS: Significant results were observed exclusively in the pediatric sample. Right prefrontal cortex thickness was positively associated with the percentage of CBT response. In a post hoc analysis, we observed that the specific changes accounting for this relationship were a higher thickness of the frontal pole and the rostral middle frontal gyrus. We observed no significant effects of age, sex, or medication on our findings. CONCLUSION: Higher cortical thickness in specific right prefrontal cortex regions may be important for CBT response in children with OCD. Our findings suggest that the right prefrontal cortex plays a relevant role in the mechanisms of action of CBT in children.