Plasmonic Aerogels as a Three-Dimensional Nanoscale Platform for Solar Fuel Photocatalysis.

We use plasmonic Au-TiO2 aerogels as a platform in which to marry synthetically thickened particle-particle junctions in TiO2 aerogel networks to Au∥TiO2 interfaces and then investigate their cooperative influence on photocatalytic hydrogen (H2) generation under both broadband (i.e., UV + visible light) and visible-only excitation. In doing so, we elucidate the dual functions that incorporated Au can play as a water reduction cocatalyst and as a plasmonic sensitizer. We also photodeposit non-plasmonic Pt cocatalyst nanoparticles into our composite aerogels in order to leverage the catalytic water-reducing abilities of Pt. This Au-TiO2/Pt arrangement in three dimensions effectively utilizes conduction-band electrons injected into the TiO2 aerogel network upon exciting the Au SPR at the Au∥TiO2 interface. The extensive nanostructured high surface-area oxide network in the aerogel provides a matrix that spatially separates yet electrochemically connects plasmonic nanoparticle sensitizers and metal nanoparticle catalysts, further enhancing solar-fuels photochemistry. We compare the photocatalytic rates of H2 generation with and without Pt cocatalysts added to Au-TiO2 aerogels and demonstrate electrochemical linkage of the SPR-generated carriers at the Au∥TiO2 interfaces to downfield Pt nanoparticle cocatalysts. Finally, we investigate visible light-stimulated generation of conduction band electrons in Au-TiO2 and TiO2 aerogels using ultrafast visible pump/IR probe spectroscopy. Substantially more electrons are produced at Au-TiO2 aerogels due to the incorporated SPR-active Au nanoparticle, whereas the smaller population of electrons generated at Au-free TiO2 aerogels likely originate at shallow traps in the high surface-area mesoporous aerogel.

Transfer of Chemically Modified Graphene with Retention of Functionality for Surface Engineering.

Single-layer graphene chemically reduced by the Birch process delaminates from a Si/SiOx substrate when exposed to an ethanol/water mixture, enabling transfer of chemically functionalized graphene to arbitrary substrates such as metals, dielectrics, and polymers. Unlike in previous reports, the graphene retains hydrogen, methyl, and aryl functional groups during the transfer process. This enables one to functionalize the receiving substrate with the properties of the chemically modified graphene (CMG). For instance, magnetic force microscopy shows that the previously reported magnetic properties of partially hydrogenated graphene remain after transfer. We also transfer hydrogenated graphene from its copper growth substrate to a Si/SiOx wafer and thermally dehydrogenate it to demonstrate a polymer- and etchant-free graphene transfer for potential use in transmission electron microscopy. Finally, we show that the Birch reduction facilitates delamination of CMG by weakening van der Waals forces between graphene and its substrate.

Laboratory technology and cosmochemistry.

Recent developments in analytical instrumentation have led to revolutionary discoveries in cosmochemistry. Instrumental advances have been made along two lines: (i) increase in spatial resolution and sensitivity of detection, allowing for the study of increasingly smaller samples, and (ii) increase in the precision of isotopic analysis that allows more precise dating, the study of isotopic heterogeneity in the Solar System, and other studies. A variety of instrumental techniques are discussed, and important examples of discoveries are listed. Instrumental techniques and instruments include the ion microprobe, laser ablation gas MS, Auger EM, resonance ionization MS, accelerator MS, transmission EM, focused ion-beam microscopy, atom probe tomography, X-ray absorption near-edge structure/electron loss near-edge spectroscopy, Raman microprobe, NMR spectroscopy, and inductively coupled plasma MS.

Establishing a molecular relationship between chondritic and cometary organic solids.

Multidimensional solid-state NMR spectroscopy is used to refine the identification and abundance determination of functional groups in insoluble organic matter (IOM) isolated from a carbonaceous chondrite (Murchison, CM2). It is shown that IOM is composed primarily of highly substituted single ring aromatics, substituted furan/pyran moieties, highly branched oxygenated aliphatics, and carbonyl groups. A pathway for producing an IOM-like molecular structure through formaldehyde polymerization is proposed and tested experimentally. Solid-state (13)C NMR analysis of aqueously altered formaldehyde polymer reveals considerable similarity with chondritic IOM. Carbon X-ray absorption near edge structure spectroscopy of formaldehyde polymer reveals the presence of similar functional groups across certain Comet 81P/Wild 2 organic solids, interplanetary dust particles, and primitive IOM. Variation in functional group concentration amongst these extraterrestrial materials is understood to be a result of various degrees of processing in the parent bodies, in space, during atmospheric entry, etc. These results support the hypothesis that chondritic IOM and cometary refractory organic solids are related chemically and likely were derived from formaldehyde polymer. The fine-scale morphology of formaldehyde polymer produced in the experiment reveals abundant nanospherules that are similar in size and shape to organic nanoglobules that are ubiquitous in primitive chondrites.

Variations of organic functional chemistry in carbonaceous matter from the asteroid 162173 Ryugu.

Primordial carbon delivered to the early earth by asteroids and meteorites provided a diverse source of extraterrestrial organics from pre-existing simple organic compounds, complex solar-irradiated macromolecules, and macromolecules from extended hydrothermal processing. Surface regolith collected by the Hayabusa2 spacecraft from the carbon-rich asteroid 162173 Ryugu present a unique opportunity to untangle the sources and processing history of carbonaceous matter. Here we show carbonaceous grains in Ryugu can be classified into three main populations defined by spectral shape: Highly aromatic (HA), Alkyl-Aromatic (AA), and IOM-like (IL). These carbon populations may be related to primordial chemistry, since C and N isotopic compositions vary between the three groups. Diffuse carbon is occasionally dominated by molecular carbonate preferentially associated with coarse-grained phyllosilicate minerals. Compared to related carbonaceous meteorites, the greater diversity of organic functional chemistry in Ryugu indicate the pristine condition of these asteroid samples.

Atomically Precise Detection and Manipulation of Nitrogen-Vacancy Centers in Nanodiamonds.

Nitrogen-vacancy (NV) centers in nanodiamonds are a promising quantum communication system offering robust and discrete single photon emission, but a more thorough understanding of properties of the NV centers is critical for real world implementation in functional devices. The first step to understanding how factors such as surface, depth, and charge state affect NV center properties is to directly characterize these defects on the atomic scale. Here we use Angstrom-resolution scanning transmission electron microscopy (STEM) to identify a single NV center in a ∼4 nm natural nanodiamond through simultaneous acquisition of electron energy loss and energy dispersive X-ray spectra, which provide a characteristic NV center peak and a nitrogen peak, respectively. In addition, we identify NV centers in larger, ∼15 nm synthetic nanodiamonds, although without the single-defect resolution afforded by the lower background of the smaller natural nanodiamonds. We have further demonstrated the potential to directly position these technologically relevant defects at the atomic scale using the scanning electron beam to "herd" NV centers and nitrogen atoms across their host nanodiamonds.

Hydrogen-bearing vesicles in space weathered lunar calcium-phosphates.

Water on the surface of the Moon is a potentially vital resource for future lunar bases and longer-range space exploration. Effective use of the resource depends on developing an understanding of where and how within the regolith the water is formed and retained. Solar wind hydrogen, which can form molecular hydrogen, water and/or hydroxyl on the lunar surface, reacts and is retained differently depending on regolith mineral content, thermal history, and other variables. Here we present transmission electron microscopy analyses of Apollo lunar soil 79221 that reveal solar-wind hydrogen concentrated in vesicles as molecular hydrogen in the calcium-phosphates apatite and merrillite. The location of the vesicles in the space weathered grain rims offers a clear link between the vesicle contents and solar wind irradiation, as well as individual grain thermal histories. Hydrogen stored in grain rims is a source for volatiles released in the exosphere during impacts.

Divalent-anion salt effects in polyelectrolyte multilayer depositions.

We systematically investigate the effects of divalent anions on the assembly of polyelectrolyte multilayers by fabricating polystyrene sulfonate (PSS)/polyallylamine hydrochloride (PAH) multilayer films from aqueous solutions containing SO(4)(2-), HPO(4)(2-), or organic dicarboxylate dianions. The chosen concentrations of these anions (i.e., ≤0.05 M) allow us to isolate their effects on the assembly process from those of the polyelectrolyte solubility or solution ionic strength (maintained constant at µ = 1.00 M by added NaCl). Compared to a control film prepared from solutions containing only Cl(-) anions, stratified multilayers deposited in the presence of dianions exhibit increased UV absorbance, thickness, and roughness. From the dependence of film properties on the solution concentration of SO(4)(2-) and number of polyelectrolyte layers deposited, we derive a generic model for the PSS/PAH multilayer formation that involves adsorption of PAH aggregates formed in solution via electrostatic interactions of PAH with bridging dianions. Experiments using HPO(4)(2-) and organic dicarboxylate species of varying structure indicate that the separation, rigidity, and angle between the discrete negatively charged sites in the dianion govern the formation of the PAH aggregates, and therefore also the properties of the multilayer film. A universal linear relationship between film UV absorbance and thickness is observed among all dianion types or concentrations, consistent with the model.

Room-Temperature Oxygen Transport in Nanothin BixOySez Enables Precision Modulation of 2D Materials.

Oxygen conductors and transporters are important to several consequential renewable energy technologies, including fuel cells and syngas production. Separately, monolayer transition-metal dichalcogenides (TMDs) have demonstrated significant promise for a range of applications, including quantum computing, advanced sensors, valleytronics, and next-generation optoelectronics. Here, we synthesize a few-nanometer-thick BixOySez compound that strongly resembles a rare R3m bismuth oxide (Bi2O3) phase and combine it with monolayer TMDs, which are highly sensitive to their environment. We use the resulting 2D heterostructure to study oxygen transport through BixOySez into the interlayer region, whereby the 2D material properties are modulated, finding extraordinarily fast diffusion near room temperature under laser exposure. The oxygen diffusion enables reversible and precise modification of the 2D material properties by controllably intercalating and deintercalating oxygen. Changes are spatially confined, enabling sub-micrometer features (e.g., pixels), and are long-term stable for more than 221 days. Our work suggests few-nanometer-thick BixOySez is a promising unexplored room-temperature oxygen transporter. Additionally, our findings suggest that the mechanism can be applied to other 2D materials as a generalized method to manipulate their properties with high precision and sub-micrometer spatial resolution.

Laser-Patterned Submicrometer Bi2Se3-WS2 Pixels with Tunable Circular Polarization at Room Temperature.

Characterizing and manipulating the circular polarization of light is central to numerous emerging technologies, including spintronics and quantum computing. Separately, monolayer tungsten disulfide (WS2) is a versatile material that has demonstrated promise in a variety of applications, including single photon emitters and valleytronics. Here, we demonstrate a method to tune the photoluminescence (PL) intensity (factor of ×161), peak position (38.4 meV range), circular polarization (39.4% range), and valley polarization of a Bi2Se3-WS2 2D heterostructure using a low-power laser (0.762 µW) in ambient conditions. Changes are spatially confined to the laser spot, enabling submicrometer (814 nm) features, and are long-term stable (>334 days). PL and valley polarization changes can be controllably reversed through laser exposure in a vacuum, allowing the material to be erased and reused. Atmospheric experiments and first-principles calculations indicate oxygen diffusion modulates the exciton radiative vs nonradiative recombination pathways, where oxygen absorption leads to brightening and desorption to darkening.

Phase Identification and Ordered Vacancy Imaging in Epitaxial Metallic Ta2N Thin Films.

Epitaxial transition metal nitrides (TMNs) are an emerging class of crystalline thin film metals that can be heteroepitaxially integrated with common group III-nitride semiconductors such as GaN and AlN. Within a binary family of TMN compounds (i.e., TaxNy), several phases typically exist, many with similar crystal structures that are difficult to distinguish by conventional X-ray diffraction or other bulk characterization means. In this work, we demonstrate the combined power of high-resolution transmission and aberration-corrected scanning transmission electron microscopy for definitive phase identification of tantalum nitrides with different N-sublattice ordering. Analysis of molecular beam epitaxy-grown γ-Ta2N films on SiC substrates shows that the films are γ phase, threading dislocation-free, and Ta-deficient. The lack of Ta manifests as ordered Ta vacancy planar defects oriented in the plane perpendicular to the [0001] growth direction and accounts for the substoichiometry. Optimization of the growth parameters should reduce the Ta vacancy concentration, and alternatively, exploitation of the attractive nature of the Ta vacancies may enable novel planar structures. These findings serve as an important first step in applying this epitaxial TMN material for new electronic and superconducting device structures.

Epitaxial bulk acoustic wave resonators as highly coherent multi-phonon sources for quantum acoustodynamics.

Solid-state quantum acoustodynamic (QAD) systems provide a compact platform for quantum information storage and processing by coupling acoustic phonon sources with superconducting or spin qubits. The multi-mode composite high-overtone bulk acoustic wave resonator (HBAR) is a popular phonon source well suited for QAD. However, scattering from defects, grain boundaries, and interfacial/surface roughness in the composite transducer severely limits the phonon relaxation time in sputter-deposited devices. Here, we grow an epitaxial-HBAR, consisting of a metallic NbN bottom electrode and a piezoelectric GaN film on a SiC substrate. The acoustic impedance-matched epi-HBAR has a power injection efficiency >99% from transducer to phonon cavity. The smooth interfaces and low defect density reduce phonon losses, yielding (f × Q) and phonon lifetimes up to 1.36 × 1017 Hz and 500 µs respectively. The GaN/NbN/SiC epi-HBAR is an electrically actuated, multi-mode phonon source that can be directly interfaced with NbN-based superconducting qubits or SiC-based spin qubits.

Stabilization of reduced copper on ceria aerogels for CO oxidation.

Photodeposition of Cu nanoparticles on ceria (CeO2) aerogels generates a high surface area composite material with sufficient metallic Cu to exhibit an air-stable surface plasmon resonance. We show that balancing the surface area of the aerogel support with the Cu weight loading is a critical factor in retaining stable Cu0. At higher Cu weight loadings or with a lower support surface area, Cu aggregation is observed by scanning and transmission electron microscopy. Analysis of Cu/CeO2 using X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy finds a mixture of Cu2+, Cu+, and Cu0, with Cu+ at the surface. At 5 wt% Cu, Cu/CeO2 aerogels exhibit high activity for heterogeneous CO oxidation catalysis at low temperatures (94% conversion of CO at 150 °C), substantially out-performing Cu/TiO2 aerogel catalysts featuring the same weight loading of Cu on TiO2 (20% conversion of CO at 150 °C). The present study demonstrates an extension of our previous concept of stabilizing catalytic Cu nanoparticles in low oxidation states on reducing, high surface area aerogel supports. Changing the reducing power of the support modulates the catalytic activity of mixed-valent Cu nanoparticles and metal oxide support.

Power of Aerogel Platforms to Explore Mesoscale Transport in Catalysis.

We describe the opportunity to deploy aerogels-an ultraporous nanoarchitecture with co-continuous networks of meso/macropores and covalently bonded nanoparticulates-as a platform to address the nature of the electronic, ionic, and mass transport that underlies catalytic activity. As a test case, we fabricated Au||TiO2 junctions in composite guest-host aerogels in which ∼5 nm Au nanoparticles are incorporated either directly into the anatase TiO2 network (Au "in" TiO2, AuIN-TiO2 aerogel) or deposited onto preformed TiO2 aerogel (Au "on" TiO2, AuON/TiO2 aerogel). The metal-meets-oxide nanoscale interphase as visualized by electron tomography feature extended three-dimensional (3D) interfaces, but AuIN-TiO2 aerogels impose a greater degree of Au contact with TiO2 particles than does the AuON/TiO2 form. Both aerogel variants enable transport of electrons over micrometer-scale distances across the TiO2 network to Au||TiO2 junctions, as evidenced by electron paramagnetic resonance (EPR) and ultrafast visible pump-IR probe time-resolved absorption spectroscopy. The siting of gold nanoparticles in the TiO2 network more effectively disperses trapped electrons. Density functional theory (DFT) calculations find that increased physical contact between Au and TiO2, induced by oxygen vacancies, produces increased hybridization of midgap states and quenches unpaired trapped electrons. We assign the apparent differences in electron-transport capabilities to a combination of the relatively better-wired Au||TiO2 junctions in AuIN-TiO2 aerogels, which have a greater capacity to dilute accumulated charge over a larger interfacial surface area, with an enhanced ability to discharge the accumulated electrons via catalytic reduction of adsorbed O2 to O2- at the interface. Solid-state 1H nuclear magnetic resonance experiments show that proton spin-lattice relaxation times and possibly proton diffusion are strongly coupled to Au||TiO2 interfacial design, likely through spin coupling of protons to unpaired electrons trapped at the TiO2 network. Taken together, our results show that Au||TiO2 interfacial design strongly impacts charge carrier (electron and proton) transport over mesoscale distances in catalytic aerogel architectures.

Enabling remote quantum emission in 2D semiconductors via porous metallic networks.

Here we report how two-dimensional crystal (2DC) overlayers influence the recrystallization of relatively thick metal films and the subsequent synergetic benefits this provides for coupling surface plasmon-polaritons (SPPs) to photon emission in 2D semiconductors. We show that annealing 2DC/Au films on SiO2 results in a reverse epitaxial process where initially nanocrystalline Au films gain texture, crystallographically orient with the 2D crystal overlayer, and form an oriented porous metallic network (OPEN) structure in which the 2DC can suspend above or coat the inside of the metal pores. Both laser excitation and exciton recombination in the 2DC semiconductor launch propagating SPPs in the OPEN film. Energy in-/out- coupling occurs at metal pore sites, alleviating the need for dielectric spacers between the metal and 2DC layer. At low temperatures, single-photon emitters (SPEs) are present across an OPEN-WSe2 film, and we demonstrate remote SPP-mediated excitation of SPEs at a distance of 17 µm.

Spatially Resolved Chemical Analysis of Geobacter sulfurreducens Cell Surface.

Geobacter sulfurreducens is of interest for the highest efficiency of power generation and extremely long extracellular electron transfer (EET) between the bacterium and electrodes. Despite more than 15 years of intensive molecular biological research, there is still no clear answer which molecules are responsible for these processes. In the present work, we look at the problem from another (atomic) perspective and identify the location and shape of the compounds that are known to be conductive, particularly those containing Fe atoms. By using highly sophisticated energy dispersive X-ray spectroscopy combined with high-angle annular dark-field transmission electron microscopy enabling detection, identification, and localization of chemical compounds on the surface at nearly atomic spatial resolution, we analyze Fe spatial distribution within the G. sulfurreducens community. We discover the presence of small Fe-containing particles on the surface of the bacterium cells. The size of the particles (diameter 5.6 nm) is highly reproducible and comparable with the size of a single protein. The particles cover about 2% of the cell surface, which is similar to that expected for molecular conductors responsible for electron transfer through the bacterium cell wall. We find that G. sulfurreducens filaments ("bacterial molecular wires") also contain Fe atoms in their bundles. We observe that the bacterium enable changing the distance between the Fe-containing bundles in the filaments from separated to attached (the latter is needed for the efficient electron transfer between the Fe-containing particles), depending on the bacterium metabolic activity and attachment to extracellular substrates. These results are consistent with the recently published research about the role of Fe atoms in protein molecular conductance ( Phys. Chem. Chem. Phys. , 2018 , 20 , 14072 - 14081 ) and show what type of Fe-containing particles are involved in the bacterial extracellular communication. They can be used for the design and construction of artificial biomolecular wires and bioinorganic interfaces.

Effects of a Lead Chloride Shell on Lead Sulfide Quantum Dots.

The size of a quantum-confined nanocrystal determines the energies of its excitonic transitions. Previous work has correlated the diameters of PbS nanocrystals to their excitonic absorption; however, we observe that PbS quantum dots synthesized in saturated dispersions of PbCl2 can deviate from the previous 1Sh-1Se energy vs diameter curve by 0.8 nm. In addition, their surface differs chemically from that of PbS quantum dots produced via other syntheses. We find that these nanocrystals are coated in a shell that is measurable in transmission electron micrographs and contains lead and chlorine, beyond the monatomic chlorine termination previously proposed. This finding has implications for understanding the growth mechanism of this reaction, the line width of these quantum dots' photoluminescence, and electronic transport within films of these nanocrystals. Such fundamental knowledge is critical to applications of PbS quantum dots such as single-photon sources, photodetectors, solar cells, light-emitting diodes, lasers, and biological labels.

Controlling the Infrared Dielectric Function through Atomic-Scale Heterostructures.

Surface phonon polaritons (SPhPs), the surface-bound electromagnetic modes of a polar material resulting from the coupling of light with optic phonons, offer immense technological opportunities for nanophotonics in the infrared (IR) spectral region. However, once a particular material is chosen, the SPhP characteristics are fixed by the spectral positions of the optic phonon frequencies. Here, we provide a demonstration of how the frequency of these optic phonons can be altered by employing atomic-scale superlattices (SLs) of polar semiconductors using AlN/GaN SLs as an example. Using second harmonic generation (SHG) spectroscopy, we show that the optic phonon frequencies of the SLs exhibit a strong dependence on the layer thicknesses of the constituent materials. Furthermore, new vibrational modes emerge that are confined to the layers, while others are centered at the AlN/GaN interfaces. As the IR dielectric function is governed by the optic phonon behavior in polar materials, controlling the optic phonons provides a means to induce and potentially design a dielectric function distinct from the constituent materials and from the effective-medium approximation of the SL. We show that atomic-scale AlN/GaN SLs instead have multiple Reststrahlen bands featuring spectral regions that exhibit either normal or extreme hyperbolic dispersion with both positive and negative permittivities dispersing rapidly with frequency. Apart from the ability to engineer the SPhP properties, SL structures may also lead to multifunctional devices that combine the mechanical, electrical, thermal, or optoelectronic functionality of the constituent layers. We propose that this effort is another step toward realizing user-defined, actively tunable IR optics and sources.

High Abundances of Presolar Grains and 15N-rich Organic Matter in CO3.0 Chondrite Dominion Range 08006.

NanoSIMS C-, N-, and O-isotopic mapping of matrix in CO3.0 chondrite Dominion Range (DOM) 08006 revealed it to have in its matrix the highest abundance of presolar O-rich grains (257 +76/-96 ppm, 2σ) of any meteorite. It also has a matrix abundance of presolar SiC of 35 (+25/-17, 2σ) ppm, similar to that seen across primitive chondrite classes. This provides additional support to bulk isotopic and petrologic evidence that DOM 08006 is the most primitive known CO meteorite. Transmission electron microscopy of five presolar silicate grains revealed one to have a composite mineralogy similar to larger amoeboid olivine aggregates and consistent with equilibrium condensation, two non-stoichiometric amorphous grains and two olivine grains, though one is identified as such solely based on its composition. We also found insoluble organic matter (IOM) to be present primarily as sub-micron inclusions with ranges of C- and N-isotopic anomalies similar to those seen in primitive CR chondrites and interplanetary dust particles. In contrast to other primitive extraterrestrial materials, H isotopic imaging showed normal and homogeneous D/H. Most likely, DOM 08006 and other CO chondrites accreted a similar complement of primitive and isotopically anomalous organic matter to that found in other chondrite classes and IDPs, but the very limited amount of thermal metamorphism experienced by DOM 08006 has caused loss of D-rich organic moieties, while not substantially affecting either the molecular carriers of C and N anomalies or most inorganic phases in the meteorite. One C-rich grain that was highly depleted in 13C and 15N was identified; we propose it originated in the Sun's parental molecular cloud.