Optical Memory, Switching, and Neuromorphic Functionality in Metal Halide Perovskite Materials and Devices.

Metal halide perovskite based materials have emerged over the past few decades as remarkable solution-processable optoelectronic materials with many intriguing properties and potential applications. These emerging materials have recently been considered for their promise in low-energy memory and information processing applications. In particular, their large optical cross-sections, high photoconductance contrast, large carrier-diffusion lengths, and mixed electronic/ionic transport mechanisms are attractive for enabling memory elements and neuromorphic devices that are written and/or read in the optical domain. Here, recent progress toward memory and neuromorphic functionality in metal halide perovskite materials and devices where photons are used as a critical degree of freedom for switching, memory, and neuromorphic functionality is reviewed.

All-atmospheric fabrication of Ag-Cu core-shell nanowire transparent electrodes with Haacke figure of merit >600 × 10-3 Ω-1.

Transparent conducting electrodes (TCEs) are essential components in devices such as touch screens, smart windows, and photovoltaics. Metal nanowire networks are promising next-generation TCEs, but best-performing examples rely on expensive metal catalysts (palladium or platinum), vacuum processing, or transfer processes that cannot be scaled. This work demonstrates a metal nanowire TCE fabrication process that focuses on high performance and simple fabrication. Here we combined direct and plating metallization processes on electrospun nanowires. We first directly metallize silver nanowires using reactive silver ink. The silver catalyzes subsequent copper plating to produce Ag-Cu core-shell nanowires and eliminates nanowire junction resistances. The process allows for tunable transmission and sheet resistance properties by adjusting electrospinning and plating time. We demonstrate state-of-the-art, low-haze TCEs using an all-atmospheric process with sheet resistances of 0.33 Ω sq-1 and visible light transmittances of 86% (including the substrate), leading to a Haacke figure of merit of 652 × 10-3 Ω-1. The core-shell nanowire electrode also demonstrates high chemical and bending durability.

Comparison of assessment of coagulation in healthy dogs by the TEG 6s and TEG 5000 viscoelastic analyzers.

The TEG 6s (Haemonetics) point-of-care viscoelastic analyzer is portable, compact, simple to use, and has the potential for rapid viscoelastic analysis that can guide the treatment of veterinary patients at the site of care. Although approved for use in people, the TEG 6s has yet to be evaluated for hemostatic analysis in veterinary medicine. Citrated whole blood (CWB) was collected from 27 healthy dogs. An aliquot of CWB from each dog was diluted by 33% with an isotonic crystalloid, representing an in vitro model of hemodilution. Unaltered and diluted CWB samples were analyzed using 2 TEG 6s and 6 TEG 5000 (Haemonetics) analyzers. The 6 TEG 5000 analyzers ran duplicate analyses of either unaltered or diluted samples using 1 of 3 reagents (Haemonetics): Kaolin TEG, RapidTEG, or TEG Functional Fibrinogen. Duplicate TEG 5000 analyses were averaged and compared with a single TEG 6s analysis. Lin concordance correlation coefficient and Bland-Altman plots were used to evaluate agreement of reaction time, kinetic time, alpha angle, maximum amplitude (MA), and G value (G) for samples activated with Kaolin TEG, and agreement of MA for samples activated with RapidTEG between the 2 machines. Overall, agreement between the TEG 6s and TEG 5000 analyzers was poor. Viscoelastic measurements by the TEG 6s and TEG 5000 in healthy dogs were not all interchangeable. Agreement was satisfactory only for MA and G measurements of diluted blood samples activated with Kaolin TEG, and MA measurements for both unaltered and diluted blood samples activated with RapidTEG.

Reversible Methanolation of Metal Halide Perovskites.

The low formation energies inherent in metal halide perovskites enable the structure to be easily broken and remade with little energy input. In this work, we leverage low formation energy to demonstrate 0D/3D structural transformations induced by reversible intercalation of methanol to yield dramatic control of visible light absorption. We identify a methanolated structure that features sheets of 0D isolated [PbI6]4- octahedra separated by MAI and methanol. Methanol and water reversibly displace each other in the 0D complex by controlling the chemical potential of the system via Le Chatelier's principle. The weaker H-bonding of methanol compared to water effectively reduces the complex dissociation temperature from 70 to 50 °C, rendering the methanol complex more desirable for an array of next-generation applications spanning low-power-consumption memory to switchable photovoltaics.

Temperature Coefficients of Perovskite Photovoltaics for Energy Yield Calculations.

Temperature coefficients for maximum power (T PCE), open circuit voltage (V OC), and short circuit current (J SC) are standard specifications included in data sheets for any commercially available photovoltaic module. To date, there has been little work on determining the T PCE for perovskite photovoltaics (PV). We fabricate perovskite solar cells with a T PCE of -0.08 rel %/°C and then disentangle the temperature-dependent effects of the perovskite absorber, contact layers, and interfaces by comparing different device architectures and using drift-diffusion modeling. A main factor contributing to the small T PCE of perovskites is their low intrinsic carrier concentrations with respect to Si and GaAs, which can be explained by its wider band gap. We demonstrate that the unique increase in E g with increasing temperatures seen for perovskites results in a reduction in J SC but positively influences V OC. The current limiting factors for the T PCE in perovskite PV are identified to originate from interfacial effects.

Reversible multicolor chromism in layered formamidinium metal halide perovskites.

Metal halide perovskites feature crystalline-like electronic band structures and liquid-like physical properties. The crystal-liquid duality enables optoelectronic devices with unprecedented performance and a unique opportunity to chemically manipulate the structure with low energy input. In this work, we leverage the low formation energy of metal halide perovskites to demonstrate multicolor reversible chromism. We synthesized layered Ruddlesden-Popper FAn+1PbnX3n+1 (FA = formamidinium, X = I, Br; n = number of layers = 1, 2, 3 … ∞) and reversibly tune the dimensionality (n) by modulating the strength and number of H-bonds in the system. H-bonding was controlled by exposure to solvent vapor (solvatochromism) or temperature change (thermochromism), which shuttles FAX salt pairs between the FAn+1PbnX3n+1 domains and adjacent FAX "reservoir" domains. Unlike traditional chromic materials that only offer a single-color transition, FAn+1PbnX3n+1 films reversibly switch between multiple colors including yellow, orange, red, brown, and white/colorless. Each colored phase exhibits distinct optoelectronic properties characteristic of 2D superlattice materials with tunable quantum well thickness.

Strategies to Achieve High Circularly Polarized Luminescence from Colloidal Organic-Inorganic Hybrid Perovskite Nanocrystals.

Colloidal metal halide perovskite nanocrystals (NCs) with chiral ligands are outstanding candidates as a circularly polarized luminescence (CPL) light source due to many advantages such as high photoluminescence quantum efficiency, large spin-orbit coupling, and extensive tunability via composition and choice of organic ligands. However, achieving pronounced and controllable polarized light emission remains challenging. Here, we develop strategies to achieve high CPL responses from colloidal formamidinium lead bromide (FAPbBr3) NCs at room temperature using chiral surface ligands. First, we show that replacing a portion of typical ligands (oleylamine) with short chiral ligands ((R)-2-octylamine) during FAPbBr3 NC synthesis results in small and monodisperse NCs that yield high CPL with average luminescence dissymmetry g-factor, glum = 6.8 × 10-2. To the best of our knowledge, this is the highest among reported perovskite materials at room temperature to date and represents around 10-fold improvement over the previously reported colloidal CsPbClxBryI3-x-y NCs. In order to incorporate NCs into any optoelectronic or spintronic application, the NCs necessitate purification, which removes a substantial amount of the chiral ligands and extinguishes the CPL signals. To circumvent this issue, we also developed a postsynthetic ligand treatment using a different chiral ligand, (R-/S-)methylbenzylammonium bromide, which also induces a CPL with an average glum = ±1.18 × 10-2. This postsynthetic method is also amenable for long-range charge transport since methylbenzylammonium is quite compact in relation to other surface ligands. Our demonstrations of high CPL and glum from both as-synthesized and purified perovskite NCs at room temperature suggest a route to demonstrate colloidal NC-based spintronics.

Characteristics associated with bacterial growth in urine in 451 proteinuric dogs (2008-2018).

BACKGROUND: Urine cultures are frequently recommended to rule out infection as a postrenal cause of proteinuria. OBJECTIVE: Identify characteristics associated with bacterial growth in urine in proteinuric dogs. ANIMALS: Four hundred and fifty-one dogs admitted to a teaching hospital between January 2008 and January 2018 with urine protein-to-creatinine ratios (UPCs) >0.5. METHODS: Retrospective study included dogs with a UPC, urinalysis, and quantitative urine culture (QUC) performed within a 72-hour period by searching electronic records. Dogs with recent antimicrobial therapy, urine collected by methods other than cystocentesis, or UPC ≤0.5 were excluded. Signalment, comorbidities, serum BUN and creatinine concentrations, urinalysis findings, and QUC results were recorded. The association between these characteristics and presence of bacterial growth in urine was assessed by univariable and multivariable analysis. RESULTS: Thirty of four hundred fifty-one dogs (6.7%) had bacterial growth in urine. Of these, 18 (60.0%) had active urine sediment. Bacterial growth in urine was associated with pyuria (odd ratio [OR] 25.1, 95% confidence interval [CI] 7.9-79.6, P < .001), bacteriuria (OR 11.1, 95% CI 3.2-39.1, P < .001), and lower urinary tract disease (OR 6.7, 95% CI 1.9-23.0; P = .0028). If QUC was prompted based on these criteria, 8/451 (1.8%) of proteinuric dogs would have had undetected bacterial growth. CONCLUSIONS AND CLINICAL IMPORTANCE: The proportion of proteinuric dogs with both inactive urine sediment and bacterial growth in urine was low, suggesting that QUC might not be necessary in the evaluation of all proteinuric dogs. An active urine sediment or lower urinary tract disease should prompt QUC for proteinuric dogs.

Vaccine safety studies of Brucella abortus S19 and S19ΔvjbR in pregnant swine.

Brucellosis in swine is caused by Brucella suis, a bacterial infection of nearly worldwide distribution. Brucella suis is also transmissible to humans, dogs and cattle and is considered a reemerging disease of public health concern. To date, there is no effective vaccine for swine. This prompted us to investigate the potential use of the commercially available vaccine for cattle or the live attenuated vaccine candidate S19ΔvjbR. As the first step, we sought to study the safety of the vaccine candidates when administered in pregnant sows, since one of the major drawbacks associated with vaccination using Live Attenuated Vaccines (LAV) is the induction of abortions when administered in pregnant animals. Fifteen pregnant gilts at mid-gestation were divided into four groups and subsequently vaccinated subcutaneously using different formulations containing 2.0 ±â€¯0.508 × 109 CFU of either S19 or S19ΔvjbR. Vaccination in pregnant animals with the vaccine candidates did not induce abortion, stillbirths or a reduction in litter size. Multiple tissues in the gilts and piglets were examined at the time of delivery to assess bacterial colonization and histopathological changes. There was no evidence of vaccine persistence in the gilts or bacterial colonization in the fetuses. Altogether, these data suggest that both vaccine candidates are safe for use in pregnant swine. Analysis of the humoral responses, specifically anti-Brucella IgG levels measured in serum, demonstrated a robust response induced by either vaccine, but of shorter duration (4-6 weeks post-inoculation) compared to that observed in cattle or experimentally infected mice. Such a transient humoral response may prove to be beneficial in cases where the vaccine is used in eradication campaigns and in the differentiation of vaccinated from infected animals. This study provides evidence to support future efficacy studies of both vaccine candidates in swine.

Atomically Thin Metal Sulfides.

We developed a method to colloidally synthesize atomically thin metal sulfides (ATMS). Unlike conventional 2D systems such as MoS2 and graphene, none of the systems developed here are inherently layered compounds nor have known layered polymorphs in their bulk forms. The synthesis proceeds via a cation-exchange reaction starting from single- and multi-layer Ag2S and going to various metal sulfides. The synthesized ATMS retain their size and shape during the cation-exchange reaction and are either single-layer or a few-layer, depending on the starting Ag2S samples. They have lateral dimensions on the order of 5-10 nm and are colloidally stabilized by Z- and L-type ligands. Here, we demonstrate the synthesis of single-layer and a few-layer ZnS, CdS, CoS2, and PbS. We find that the optical properties of these ATMS are quite distinct from the platelet or quantum-dot versions of the same metal sulfides.

Targeted Ligand-Exchange Chemistry on Cesium Lead Halide Perovskite Quantum Dots for High-Efficiency Photovoltaics.

The ability to manipulate quantum dot (QD) surfaces is foundational to their technological deployment. Surface manipulation of metal halide perovskite (MHP) QDs has proven particularly challenging in comparison to that of more established inorganic materials due to dynamic surface species and low material formation energy; most conventional methods of chemical manipulation targeted at the MHP QD surface will result in transformation or dissolution of the MHP crystal. In previous work, we have demonstrated record-efficiency QD solar cells (QDSCs) based on ligand-exchange procedures that electronically couple MHP QDs yet maintain their nanocrystalline size, which stabilizes the corner-sharing structure of the constituent PbI64- octahedra with optoelectronic properties optimal for solar energy conversion. In this work, we employ a variety of spectroscopic techniques to develop a molecular-level understanding of the MHP QD surface chemistry in this system. We individually target both the anionic (oleate) and cationic (oleylammonium) ligands. We find that atmospheric moisture aids the process by hydrolysis of methyl acetate to generate acetic acid and methanol. Acetic acid then replaces native oleate ligands to yield QD surface-bound acetate and free oleic acid. The native oleylammonium ligands remain throughout this film deposition process and are exchanged during a final treatment step employing smaller cations-namely, formamidinium. This final treatment has a narrow processing window; initial treatment at this stage leads to a more strongly coupled QD regime followed by transformation into a bulk MHP film after longer treatment. These insights provide chemical understanding to the deposition of high-quality, electronically coupled MHP QD films that maintain both quantum confinement and their crystalline phase and attain high photovoltaic performance.

Thermodynamic Driving Force in the Spontaneous Formation of Inorganic Nanoparticle Solutions.

Nanoparticles are the bridge between the molecular and the macroscopic worlds. The growing number of commercial applications for nanoparticles spans from consumer products to new frontiers of medicine and next-generation optoelectronic technology. They are most commonly deployed in the form of a colloid, or "ink", which are formulated with solvents, surfactants, and electrolytes to kinetically prevent the solid particulate phase from reaching the thermodynamically favored state of separate solid and liquid phases. In this work, we theoretically determine the thermodynamic requirements for forming a single-phase solution of spherical particles and engineer a model system to experimentally demonstrate the spontaneous formation of solutions composed of only solvent and bare inorganic nanoparticles. We show molecular interactions at the nanoparticle interface are the driving force in high-concentration nanoparticle solutions. The work establishes a regime where inorganic nanoparticles behave as molecular solutes as opposed to kinetically stable colloids, which has far-reaching implications for the future design and deployment of nanomaterial technologies.

Enhanced mobility CsPbI3 quantum dot arrays for record-efficiency, high-voltage photovoltaic cells.

We developed lead halide perovskite quantum dot (QD) films with tuned surface chemistry based on A-site cation halide salt (AX) treatments. QD perovskites offer colloidal synthesis and processing using industrially friendly solvents, which decouples grain growth from film deposition, and at present produce larger open-circuit voltages (VOC's) than thin-film perovskites. CsPbI3 QDs, with a tunable bandgap between 1.75 and 2.13 eV, are an ideal top cell candidate for all-perovskite multijunction solar cells because of their demonstrated small VOC deficit. We show that charge carrier mobility within perovskite QD films is dictated by the chemical conditions at the QD-QD junctions. The AX treatments provide a method for tuning the coupling between perovskite QDs, which is exploited for improved charge transport for fabricating high-quality QD films and devices. The AX treatments presented here double the film mobility, enabling increased photocurrent, and lead to a record certified QD solar cell efficiency of 13.43%.

Switchable photovoltaic windows enabled by reversible photothermal complex dissociation from methylammonium lead iodide.

Materials with switchable absorption properties have been widely used for smart window applications to reduce energy consumption and enhance occupant comfort in buildings. In this work, we combine the benefits of smart windows with energy conversion by producing a photovoltaic device with a switchable absorber layer that dynamically responds to sunlight. Upon illumination, photothermal heating switches the absorber layer-composed of a metal halide perovskite-methylamine complex-from a transparent state (68% visible transmittance) to an absorbing, photovoltaic colored state (less than 3% visible transmittance) due to dissociation of methylamine. After cooling, the methylamine complex is re-formed, returning the absorber layer to the transparent state in which the device acts as a window to visible light. The thermodynamics of switching and performance of the device are described. This work validates a photovoltaic window technology that circumvents the fundamental tradeoff between efficient solar conversion and high visible light transmittance that limits conventional semitransparent PV window designs.

Broadband Absorbing Exciton-Plasmon Metafluids with Narrow Transparency Windows.

Optical metafluids that consist of colloidal solutions of plasmonic and/or excitonic nanomaterials may play important roles as functional working fluids or as means for producing solid metamaterial coatings. The concept of a metafluid employed here is based on the picture that a single ballistic photon, propagating through the metafluid, interacts with a large collection of specifically designed optically active nanocrystals. We demonstrate water-based metafluids that act as broadband electromagnetic absorbers in a spectral range of 200-3300 nm and feature a tunable narrow (∼100 nm) transparency window in the visible-to-near-infrared region. To define this transparency window, we employ plasmonic gold nanorods. We utilize excitonic boron-doped silicon nanocrystals as opaque optical absorbers ("optical wall") in the UV and blue-green range of the spectrum. Water itself acts as an opaque "wall" in the near-infrared to infrared. We explore the limits of the concept of a "simple" metafluid by computationally testing and validating the effective medium approach based on the Beer-Lambert law. According to our simulations and experiments, particle aggregation and the associated decay of the window effect are one example of the failure of the simple metafluid concept due to strong interparticle interactions.

All-Inorganic Germanium Nanocrystal Films by Cationic Ligand Exchange.

We introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and (1)H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport in germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.

Hypervalent surface interactions for colloidal stability and doping of silicon nanocrystals.

Colloidal semiconductor nanocrystals have attracted attention for cost-effective, solution-based deposition of quantum-confined thin films for optoelectronics. However, two significant challenges must be addressed before practical nanocrystal-based devices can be realized. The first is coping with the ligands that terminate the nanocrystal surfaces. Though ligands provide the colloidal stability needed to cast thin films from solution, these ligands dramatically hinder charge carrier transport in the resulting film. Second, after a conductive film is achieved, doping has proven difficult for further control of the optoelectronic properties of the film. Here we report the ability to confront both of these challenges by exploiting the ability of silicon to engage in hypervalent interactions with hard donor molecules. For the first time, we demonstrate the significant potential of applying the interaction to the nanocrystal surface. In this study, hypervalent interactions are shown to provide colloidal stability as well as doping of silicon nanocrystals.

Tunable Band Gap Emission and Surface Passivation of Germanium Nanocrystals Synthesized in the Gas Phase.

The narrow bulk band gap and large exciton Bohr radius of germanium (Ge) make it an attractive material for optoelectronics utilizing band-gap-tunable photoluminescence (PL). However, realization of PL due to quantum confinement remains scarcely reported. Instead, PL is often observed from surface trap states and is independent of nanocrystal (NC) size. Here, we demonstrate tunable band gap PL by chemically passivating the Ge NC surface. The exchange of native Ge-Cl surface groups with alkyl groups using Grignard reagents leads to the first instance of tunable band gap emission from free-standing Ge NCs synthesized in the gas phase. Ge NCs between 4.8 and 10.2 nm in diameter exhibit near-infrared emission featuring spectral line widths that are at least a factor of 2 narrower than any previous report.