Enhancing hyperspectral EELS analysis of complex plasmonic nanostructures with pan-sharpening.

Nanoscale hyperspectral techniques-such as electron energy loss spectroscopy (EELS)-are critical to understand the optical response in plasmonic nanostructures, but as systems become increasingly complex, the required sampling density and acquisition times become prohibitive for instrumental and specimen stability. As a result, there has been a recent push for new experimental methodologies that can provide comprehensive information about a complex system, while significantly reducing the duration of the experiment. Here, we present a pan-sharpening approach to hyperspectral EELS analysis, where we acquire two datasets from the same region (one with high spatial resolution and one with high spectral fidelity) and combine them to achieve a single dataset with the beneficial properties of both. This work outlines a straightforward, reproducible pathway to reduced experiment times and higher signal-to-noise ratios, while retaining the relevant physical parameters of the plasmonic response, and is generally applicable to a wide range of spectroscopy modalities.

Adhesion and Stability of Nanocellulose Coatings on Flat Polymer Films and Textiles.

Renewable nanocellulose materials received increased attention owing to their small dimensions, high specific surface area, high mechanical characteristics, biocompatibility, and compostability. Nanocellulose coatings are among many interesting applications of these materials to functionalize different by composition and structure surfaces, including plastics, polymer coatings, and textiles with broader applications from food packaging to smart textiles. Variations in porosity and thickness of nanocellulose coatings are used to adjust a load of functional molecules and particles into the coatings, their permeability, and filtration properties. Mechanical stability of nanocellulose coatings in a wet and dry state are critical characteristics for many applications. In this work, nanofibrillated and nanocrystalline cellulose coatings deposited on the surface of polymer films and textiles made of cellulose, polyester, and nylon are studied using atomic force microscopy, ellipsometry, and T-peel adhesion tests. Methods to improve coatings' adhesion and stability using physical and chemical cross-linking with added polymers and polycarboxylic acids are analyzed in this study. The paper reports on the effect of the substrate structure and ability of nanocellulose particles to intercalate into the substrate on the coating adhesion.

Multimodal Chemical Imaging for Linking Adhesion with Local Chemistry in Agrochemical Multicomponent Polymeric Coatings.

Seed coatings improve germination and offer higher crop yields through a blend of active ingredients (such as insecticides and fungicides), polymers, waxes, fillers, and pigments. To reach their full potential, fundamental formulation challenges bridging structure and function need to be addressed. In some instances, during industrial-volume packing and transportation, coated seeds do not flow well through elevators, conveyers, and applicators, which may reduce yield and add cost. In this work, we illustrate a combinatorial chemical imaging approach to study seed coatings at the microscale to link chemical and physical properties responsible for low seed flowability. The local chemical composition was examined using time-of-flight secondary ion mass spectrometry (ToF-SIMS) and at comparable length scales, the local adhesive properties were examined using atomic force microscopy (AFM) force volume mapping. The link between the chemical and the adhesive properties was established by non-negative matrix factorization (NMF). The correlative multimodal imaging approach developed here utilizing AFM force volume mapping, ToF-SIMS chemical mapping, and data analytics offers a path for linking function with localized chemistry when investigating multicomponent soft material systems.

Probing static discharge of polymer surfaces with nanoscale resolution.

Triboelectric charging strongly affects the operation cycle and handling of materials and can be used to harvest mechanical energy through triboelectric nanogenerator set-up. Despite ubiquity of triboelectric effects, a lot of mechanisms surrounding the relevant phenomena remain to be understood. Continued progress will rely on the development of rapid and reliable methods to probe accumulation and dynamics of static charges. Here, we demonstrate in-situ quantification of tribological charging with nanoscale resolution, that is applicable to a wide range of dielectric systems. We apply this method to differentiate between strongly and weakly charging compositions of industrial grade polymers. The method highlights the complex phenomena of electrostatic discharge upon contact formation to pre-charged surfaces, and directly reveals the mobility of surface charges. Systematic characterization of commercial polyethylene terephthalate samples revealed the compositions with the best antistatic properties and provided an estimate of characteristic charge density up to 5×10^-5 C/m². Large-scale molecular dynamics simulations were used to resolve atomistic level structural and dynamical details revealing enrichment of oxygen containing groups near the air-interface where electrostatic charges are likely to accumulate.

Multi-Frequency Measurement of Volatile Organic Compounds With a Radio-Frequency Interferometer.

We present a radio-frequency (RF) sensor and its measurement results of three volatile organic compounds (VOCs) at multiple frequency points from ∼ 2 to ∼ 11 GHz, which is a convenient range in our examination. The sensor is based on a simple RF interferometer and uses two coplanar waveguides (CPWs), A and B of 5 and 25 mm length, respectively, as VOC sensing electrodes. Approximately 70-nm-thick poly copolymer films are coated on CPW surfaces for VOC adsorption and concentration. It is shown that ethanol, acetone, and isopropyl (IPA) induce frequency-dependent RF responses, which are also VOC-dependent. Thus, the frequency-dependent properties provide a possible new approach for better VOC sensing selectivity. With CPW A, the limit-of-detections (LODs) are ∼ 600 ppm for ethanol, ∼ 270 ppm for acetone, and ∼ 330 ppm for IPA at 9.29 GHz. With CPW B, the LODs are roughly four times better. These LODs are also better than most of other RF VOC sensor results. In the future work, it is promising to further improve RF sensitivity and selectivity significantly.

Kinetics of evaporation and gel formation in thin films of ceramic precursors.

Precursors derived from the hydrolysis of organic or inorganic salts have been widely used to produce ceramic coatings for a broad variety of applications. When applying the liquid precursors to the substrates, it is extremely challenging to control the film uniformity and homogeneity. The rate of solvent evaporation at different locations is different, causing the viscosity variation and flows in the film. There is very limited knowledge about the viscosity change in evaporating ceramic precursors. Therefore, it is crucial to understand the effect of evaporation on viscosity variation in thin films and droplets. We use magnetic rotational spectroscopy to study the time dependence of viscosity in mullite precursors. A correlation between the viscosity change and evaporation kinetics is revealed. This correlation was used to relate the change of viscosity to the concentration of mullite. A master curve relating viscosity to the mullite concentration was constructed and used to propose a possible scenario of the viscosity increase during solvent evaporation.

Dual-analgesic loaded UHMWPE exhibits synergistic antibacterial effects against Staphylococci.

Total joint arthroplasty is one of the most common surgeries in the United States, with almost a million procedures performed annually. Periprosthetic joint infections (PJI) remain the most devastating complications associated with total joint replacement. Effective antibacterial prophylaxis after primary arthroplasty could substantially reduce incidence rate of PJI. In the present study we propose to provide post-arthroplasty prophylaxis via dual-analgesic loaded ultra-high molecular weight polyethylene (UHMWPE). Our approach is based on previous studies that showed pronounced antibacterial activity of analgesic- and NSAID-loaded UHMWPE against Staphylococci. Here, we prepared bupivacaine/tolfenamic acid-loaded UHMWPE and assessed its antibacterial activity against Staphylococcus aureus and Staphylococcus epidermidis. Dual-drug loaded UHMWPE yielded an additional 1-2 log reduction of bacteria, when compared with single-drug loaded UHMWPE. Analysis of the drug elution kinetics suggested that the observed increase in antibacterial activity is due to the increased tolfenamic acid elution from dual-drug loaded UHMWPE. We showed that the increased fractal dimension of the drug domains in UHMWPE could be associated with increased drug elution, leading to higher antibacterial activity. Dual-analgesic loaded UHMWPE proposed here can be used as part of multi-modal antibacterial prophylaxis and promises substantial reduction in post-arthroplasty mortality and morbidity.

Highly Adhesive Antimicrobial Coatings for External Fixation Devices.

Pin site infections arise from the use of percutaneous pinning techniques (as seen in skeletal traction, percutaneous fracture pinning, and external fixation for fracture stabilization or complex deformity reconstruction). These sites are niduses for infection because the skin barrier is disrupted, allowing for bacteria to enter a previously privileged area. After external fixation, the rate of pin site infections can reach up to 100%. Following pin site infection, the pin may loosen, causing increased pain (increasing narcotic usage) and decreasing the fixation of the fracture or deformity correction construct. More serious complications include osteomyelitis and deep tissue infections. Due to the morbidity and costs associated with its sequelae, strategies to reduce pin site infections are vital. Current strategies for preventing implant-associated infections include coatings with antibiotics, antimicrobial polymers and peptides, silver, and other antiseptics like chlorhexidine and silver-sulfadiazine. Problems facing the development of antimicrobial coatings on orthopedic implants and, specifically, on pins known as Kirschner wires (or K-wires) include poor adhesion of the drug-eluting layer, which is easily removed by shear forces during the implantation. Development of highly adhesive drug-eluting coatings could therefore lead to improved antimicrobial efficacy of these devices and ultimately reduce the burden of pin site infections. In response to this need, we developed two types of gel coatings: synthetic poly-glycidyl methacrylate-based and natural-chitosan-based. Upon drying, these gel coatings showed strong adhesion to pins and remained undamaged after the application of strong shear forces. We also demonstrated that antibiotics can be incorporated into these gels, and a K-wire with such a coating retained antimicrobial efficacy after drilling into and removal from a bone. Such a coating could be invaluable for K-wires and other orthopedic implants that experience strong shear forces during their implantation.

Correlated mechanochemical maps of Arabidopsis thaliana primary cell walls using atomic force microscope infrared spectroscopy.

Spatial heterogeneity in composition and organisation of the primary cell wall affects the mechanics of cellular morphogenesis. However, directly correlating cell wall composition, organisation and mechanics has been challenging. To overcome this barrier, we applied atomic force microscopy coupled with infrared (AFM-IR) spectroscopy to generate spatially correlated maps of chemical and mechanical properties for paraformaldehyde-fixed, intact Arabidopsis thaliana epidermal cell walls. AFM-IR spectra were deconvoluted by non-negative matrix factorisation (NMF) into a linear combination of IR spectral factors representing sets of chemical groups comprising different cell wall components. This approach enables quantification of chemical composition from IR spectral signatures and visualisation of chemical heterogeneity at nanometer resolution. Cross-correlation analysis of the spatial distribution of NMFs and mechanical properties suggests that the carbohydrate composition of cell wall junctions correlates with increased local stiffness. Together, our work establishes new methodology to use AFM-IR for the mechanochemical analysis of intact plant primary cell walls.

Role of Decomposition Product Ions in Hysteretic Behavior of Metal Halide Perovskite.

Ion migration is one of the most debated mechanisms and credited with multiple observed phenomena and performance in metal halide perovskites (MHPs) semiconductor devices. However, to date, the migration of ions and their effects on MHPs are not still fully understood, largely due to a lack of direct observations of temporal ion migration. In this work, using direct observation of ion migration in-operando, we observe the hysteretic migration behavior of intrinsic ions (i.e., CH3NH3+ and I-) as well as reveal the migration behavior of CH3NH3+ decomposition ions. We find that CH3NH3+ decomposition products can be affected by light and accumulate at the interfaces under bias. These MHP decomposition products are tightly related to the device performance and stability. Complementary results of time-resolved Kelvin probe force microscopy (tr-KPFM) demonstrate a correlation between dynamics of these interfacial ions and charge carriers. Overall, we find that there are a number of mobile ions including CH3NH3+ decomposition products in MHPs that need to be taken into account when measuring MHP device responses (e.g., charge dynamics) and should be considered in future optimization studies of MHP semiconductor devices.

Microstructural Evaluation of Phase Instability in Large Bandgap Metal Halide Perovskites.

The optoelectronic performance of organic-inorganic halide perovskite (OIHP)-based devices has been improved in recent years. Particularly, solar cells fabricated using mixed-cations and mixed-halides have outperformed their single-cation and single-halide counterparts. Yet, a systematic evaluation of the microstructural behavior of mixed perovskites is missing despite their known composition-dependent photoinstability. Here, we explore microstructural inhomogeneity in (FAPbI3)x(MAPbBr3)1-x using advanced scanning probe microscopy techniques. Contact potential difference (CPD) maps measured by Kelvin probe force microscopy show an increased fraction of grains exhibiting a low CPD with flat topography as MAPbBr3 concentration is increased. The higher portion of low CPD contributes to asymmetric CPD distribution curves. Chemical analysis reveals these grains being rich in MA, Pb, and I. The composition-dependent phase segregation upon illumination, reflected on the emergence of a low-energy peak emission in the original photoluminescence spectra, arises from the formation of such grains with flat topology. Bias-dependent piezo-response force microscopy measurements, in these grains, further confirm vigorous ion migration and cause a hysteretic piezo-response. Our results, therefore, provide insights into the microstructural evaluation of phase segregation and ion migration in OIHPs pointing toward process optimization as a mean to further enhance their optoelectronic performance.

Hysteretic Ion Migration and Remanent Field in Metal Halide Perovskites.

The gap in understanding how underlying chemical dynamics impact the functionality of metal halide perovskites (MHPs) leads to the controversy about the origin of many phenomena associated with ion migration in MHPs. In particular, the debate regarding the impact of ion migration on current-voltage (I-V) hysteresis of MHPs devices has lasted for many years, where the difficulty lies in directly uncovering the chemical dynamics, as well as identifying and separating the impact of specific ions. In this work, using a newly developed time-resolved time-of-flight secondary ion mass spectrometry CH3NH3 + and I- migrations in CH3NH3PbI3 are directly observed, revealing hysteretic CH3NH3 + and I- migrations. Additionally, hysteretic CH3NH3 + migration is illumination-dependent. Correlating these results with the I-V characterization, this work uncovers that CH3NH3 + redistribution can induce a remanent field leading to a spontaneous current in the device. It unveils that the CH3NH3 + migration is responsible for the illumination-associated I-V hysteresis in MHPs. Hysteretic ion migration has not been uncovered and the contribution of any ions (e.g., CH3NH3 +) has not been specified before. Such insightful and detailed information has up to now been missing, which is critical to improving MHPs photovoltaic performance and developing MHPs-based memristors and synaptic devices.

Correlated Materials Characterization via Multimodal Chemical and Functional Imaging.

Multimodal chemical imaging simultaneously offers high-resolution chemical and physical information with nanoscale and, in select cases, atomic resolution. By coupling modalities that collect physical and chemical information, we can address scientific problems in biological systems, battery and fuel cell research, catalysis, pharmaceuticals, photovoltaics, medicine, and many others. The combined systems enable the local correlation of material properties with chemical makeup, making fundamental questions of how chemistry and structure drive functionality approachable. In this Review, we present recent progress and offer a perspective for chemical imaging used to characterize a variety of samples by a number of platforms. Specifically, we present cases of infrared and Raman spectroscopies combined with scanning probe microscopy; optical microscopy and mass spectrometry; nonlinear optical microscopy; and, finally, ion, electron, and probe microscopies with mass spectrometry. We also discuss the challenges associated with the use of data originated by the combinatorial hardware, analysis, and machine learning as well as processing tools necessary for the interpretation of multidimensional data acquired from multimodal studies.

Molecular reorganization in bulk bottlebrush polymers: direct observation via nanoscale imaging.

Bottlebrush polymers are important for a variety of applications ranging from drug delivery to electronics. The functional flexibility of the branched sidechains has unique assembly properties when compared to linear block polymer systems. However, reports of direct observation of molecular reorganization have been sparse. This information is necessary to enhance the understanding of the structure-property relationships in these systems and yield a rational design approach for novel polymeric materials. In this work, we report direct visualization of bottlebrush molecular organization and the formation of nematic-type ordering in an amorphous polymer bottlebrush system, captured with plasma etching and helium ion microscopy. By observing the unperturbed structure of this material at high resolution and quantifying image features, we were able to qualitatively link experimental results with structures predicted by coarse-grained molecular dynamics simulations. The direct visualization and computation workflow developed in this work can be applied to a broad variety of polymers with different architectures, linking imaging results with other, independent channels of information for better understanding and control of these classes of materials.

En Route to Practicality of the Polymer Grafting Technology: One-Step Interfacial Modification with Amphiphilic Molecular Brushes.

Surface modification with polymer grafting is a versatile tool for tuning the surface properties of a wide variety of materials. From a practical point of view, such a process should be readily scalable and transferable between different substrates and consist of as least number of steps as possible. To this end, a cross-linkable amphiphilic copolymer system that is able to bind covalently to surfaces and form permanently attached networks via a one-step procedure is reported here. This system consists of brushlike copolymers (molecular brushes) made of glycidyl methacrylate, poly(oligo(ethylene glycol) methyl ether methacrylate), and lauryl methacrylate, which provide the final product with tunable reactivity and balance between hydrophilicity and hydrophobicity. The detailed study of the copolymer synthesis and properties has been carried out to establish the most efficient pathway to design and tailor this amphiphilic molecular brush system for specific applications. As an example of the applications, we showed the ability to control the deposition of graphene oxide (GO) sheets on both hydrophilic and hydrophobic surfaces using GO modified with the molecular brushes. Also, the capability to tune the osteoblast cell adhesion with the copolymer-based coatings was demonstrated.

Highly Conductive and Transparent Reduced Graphene Oxide Nanoscale Films via Thermal Conversion of Polymer-Encapsulated Graphene Oxide Sheets.

Despite noteworthy progress in the fabrication of large-area graphene sheetlike nanomaterials, the vapor-based processing still requires sophisticated equipment and a multistage handling of the material. An alternative approach to manufacturing functional graphene-based films includes the employment of graphene oxide (GO) micrometer-scale sheets as precursors. However, search for a scalable manufacturing technique for the production of high-quality GO nanoscale films with high uniformity and high electrical conductivity is still continuing. Here we show that conventional dip-coating technique can offer fabrication of high quality mono- and bilayered films made of GO sheets. The method is based on our recent discovery that encapsulating individual GO sheets in a nanometer thick molecular brush copolymer layer allows for the nearly perfect formation of the GO layers via dip coating from water. By thermal reduction the bilayers (cemented by a carbon-forming polymer linker) are converted into highly conductive and transparent reduced GO films with a high conductivity up to 104 S/cm and optical transparency on the level of 90%. The value is the highest electrical conductivity reported for thermally reduced nanoscale GO films and is close to the conductivity of indium tin oxide currently in use for transparent electronic devices, thus making these layers intriguing candidates for replacement of ITO films.

Gradient Polymer Nanofoams for Encrypted Recording of Chemical Events.

We have fabricated gradient-grafted nanofoam films that are able to record the presence of volatile chemical compounds in an offline regime. In essence, the nanofoam film (100-300 nm thick) is anchored to a surface cross-linked polymer network in a metastable extended configuration that can relax back to a certain degree upon exposure to a chemical vapor. The level of the chain relaxation is associated with thermodynamic affinity between the polymer chains and the volatile compounds. In our design, the chemical composition of the nanofoam film is not uniform; therefore, the film possesses a gradually changing local affinity to a vapor along the surface. Upon vapor exposure, the nonuniform changes in local film morphology provide a permanent record or "fingerprint" for the chemical event of interest. This permanent modification in the film structure can be directly detected via changes not only in the film surface profile but also in the film optical characteristics. To this end, we demonstrated that sensing/recording nanofoam films can be prepared and interrogated on the surfaces of optical waveguides, microring optical resonators. It is important that the initial surface profile and structure of the nanofoam film are encrypted by the distinctive conditions that were used to fabricate the film and practically impossible to replicate without prior knowledge.

Electrospray Deposition of Uniform Thickness Ge23Sb7S70 and As40S60 Chalcogenide Glass Films.

Solution-based electrospray film deposition, which is compatible with continuous, roll-to-roll processing, is applied to chalcogenide glasses. Two chalcogenide compositions are demonstrated: Ge23Sb7S70 and As40S60, which have both been studied extensively for planar mid-infrared (mid-IR) microphotonic devices. In this approach, uniform thickness films are fabricated through the use of computer numerical controlled (CNC) motion. Chalcogenide glass (ChG) is written over the substrate by a single nozzle along a serpentine path. Films were subjected to a series of heat treatments between 100 °C and 200 °C under vacuum to drive off residual solvent and densify the films. Based on transmission Fourier transform infrared (FTIR) spectroscopy and surface roughness measurements, both compositions were found to be suitable for the fabrication of planar devices operating in the mid-IR region. Residual solvent removal was found to be much quicker for the As40S60 film as compared to Ge23Sb7S70. Based on the advantages of electrospray, direct printing of a gradient refractive index (GRIN) mid-IR transparent coating is envisioned, given the difference in refractive index of the two compositions in this study.

Stability of Grafted Polymer Nanoscale Films toward Gamma Irradiation.

The present article focuses on the influence of gamma irradiation on nanoscale polymer grafted films and explores avenues for improvements in their stability toward the ionizing radiation. In terms of applications, we concentrate on enrichment polymer layers (EPLs), which are polymer thin films employed in sensor devices for the detection of chemical and biological substances. Specifically, we have studied the influence of gamma irradiation on nanoscale poly(glycidyl methacrylate) (PGMA) grafted EPL films. First, it was determined that a significant level of cross-linking was caused by irradiation in pure PGMA films. The cross-linking is accompanied by the formation of conjugated ester, carbon double bonds, hydroxyl groups, ketone carbonyls, and the elimination of epoxy groups as determined by FTIR. Polystyrene, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, dimethylphenylsilanol, BaF2, and gold nanoparticles were incorporated into the films and were found to mitigate different aspects of the radiation damage.