Transforming science labs into automated factories of discovery.

Laboratories in chemistry, biochemistry, and materials science are at the leading edge of technology, discovering molecules and materials to unlock capabilities in energy, catalysis, biotechnology, sustainability, electronics, and more. Yet, most modern laboratories resemble factories from generations past, with a large reliance on humans manually performing synthesis and characterization tasks. Robotics and automation can enable scientific experiments to be conducted faster, more safely, more accurately, and with greater reproducibility, allowing scientists to tackle large societal problems in domains such as health and energy on a shorter timescale.

Fast Catalysis at Low Overpotential: Designing Efficient Dicationic Re(bpy)(CO)I Electrocatalysts for CO Reduction.

We report a series of isomeric, dicationic Re(bpy)(CO)I complexes with bpy (2,2'-bipyridine) modified by two phenyl-CH-(NMe) pendants with cations located at variable distances from the active site for electrocatalytic CO reduction in CHCN/2.8 M HO. The position of the cationic groups dramatically increases the rate of catalysis by ∼800-fold, from 1.

Covalent Functionalization of Silicon with Plasma-Grown "Fuzzy" Graphene: Robust Aqueous Photoelectrodes for CO Reduction by Molecular Catalysts.

Carbon electrodes are ideal for electrochemistry with molecular catalysts, exhibiting facile charge transfer and good stability. Yet for solar-driven catalysis with semiconductor light absorbers, stable semiconductor/carbon interfaces can be difficult to achieve, and carbon's high optical extinction means it can only be used in ultrathin layers. Here, we demonstrate a plasma-enhanced chemical vapor deposition process that achieves well-controlled deposition of out-of-plane "fuzzy" graphene (FG) on thermally oxidized Si substrates.

Understanding the Electronic Transport of Al-Si and Al-Ge Nanojunctions by Exploiting Temperature-Dependent Bias Spectroscopy.

Understanding the electronic transport of metal-semiconductor heterojunctions is of utmost importance for a wide range of emerging nanoelectronic devices like adaptive transistors, biosensors, and quantum devices. Here, we provide a comparison and in-depth discussion of the investigated Schottky heterojunction devices based on Si and Ge nanowires contacted with pure single-crystal Al. Key for the fabrication of these devices is the selective solid-state metal-semiconductor exchange of Si and Ge nanowires into Al, delivering void-free, single-crystal Al contacts with flat Schottky junctions, distinct from the bulk counterparts.

Coordination of copper within a crystalline carbon nitride and its catalytic reduction of CO.

Inherently disordered structures of carbon nitrides have hindered an atomic level tunability and understanding of their catalytic reactivity. Starting from a crystalline carbon nitride, poly(triazine imide) or PTI/LiCl, the coordination of copper cations to its intralayer -triazine groups was investigated using molten salt reactions. The reaction of PTI/LiCl within CuCl or eutectic KCl/CuCl molten salt mixtures at 280 to 450 °C could be used to yield three partially disordered and ordered structures, wherein the Cu cations are found to coordinate within the intralayer cavities.

Monolayer-like Exciton Recombination Dynamics of Multilayer MoSe Observed by Pump-Probe Microscopy.

Transition metal dichalcogenides (TMDCs) have garnered considerable interest over the past decade as a class of semiconducting layered materials. Most studies on the carrier dynamics in these materials have focused on the monolayer due to its direct bandgap, strong photoluminescence, and strongly bound excitons. However, a comparative understanding of the carrier dynamics in multilayer (e.

Epitaxially Grown Silicon Nanowires with a Gold Molecular Adhesion Layer for Core/Shell Structures with Compact Mie and Plasmon Resonances.

Noble-metal plasmonic nanostructures have attracted much attention because they can support deep-subwavelength optical resonances, yet their performance tends to be limited by high Ohmic absorption losses. In comparison, high-index dielectric materials can support low-loss optical resonances but do not tend to yield the same subwavelength optical confinement. Here, we combine these two approaches and examine the dielectric-plasmonic resonances in dielectric/metal core/shell nanowires.

Optical Nonlinearity in Silicon Nanowires Enabled by Bound States in the Continuum.

Intense electromagnetic fields localized within resonant photonic nanostructures provide versatile opportunities for engineering nonlinear optical effects on a subwavelength scale. For dielectric structures, optical bound states in the continuum (BICs, resonant nonradiative modes that exist within the radiation continuum) are an emerging strategy to localize and intensify fields. Here, we report efficient second and third harmonic generation from Si nanowires (NWs) encoded with BIC and -BIC resonances.

Multi-Electron Transfer at H-Terminated p-Si Electrolyte Interfaces: Large Photovoltages under Inversion Conditions.

Photovoltages for hydrogen-terminated p-Si(111) in an acetonitrile electrolyte were quantified with methyl viologen [1,1'-(CH)-4,4'-bipyridinium](PF), abbreviated MV, and [Ru(bpy)](PF), where bpy is 2,2'-bipyridine, that respectively undergo two and three one-electron transfer reductions. The reduction potentials, °, of the two MV reductions occurred at energies within the forbidden bandgap, while the three [Ru(bpy)] reductions occurred within the continuum of conduction band states. Bandgap illumination resulted in reduction that was more positive than that measured with a degenerately doped n-Si demonstrative of a photovoltage, , that increased in the order MV (260 mV) < MV (400 mV) < Ru (530 mV) ∼ Ru (540 mV) ∼ Ru (550 mV).

Water splitting with silicon p-i-n superlattices suspended in solution.

Photoelectrochemical (PEC) water splitting to produce hydrogen fuel was first reported 50 years ago, yet artificial photosynthesis has not become a widespread technology. Although planar Si solar cells have become a ubiquitous electrical energy source economically competitive with fossil fuels, analogous PEC devices have not been realized, and standard Si p-type/n-type (p-n) junctions cannot be used for water splitting because the bandgap precludes the generation of the needed photovoltage. An alternative paradigm, the particle suspension reactor (PSR), forgoes the rigid design in favour of individual PEC particles suspended in solution, a potentially low-cost option compared with planar systems.

Synthesis and Surface Attachment of Molecular Re(I) Complexes Supported by Functionalized Bipyridyl Ligands.

Eleven 2,2'-bipyridine (bpy) ligands functionalized with attachment groups for covalent immobilization on silicon surfaces were prepared. Five of the ligands feature silatrane functional groups for attachment to metal oxide coatings on the silicon surfaces, while six contain either alkene or alkyne functional groups for attachment to hydrogen-terminated silicon surfaces. The bpy ligands were coordinated to Re(CO)Cl to form complexes of the type Re(bpy)(CO)Cl, which are related to known catalysts for CO reduction.

Aqueous Photoelectrochemical CO Reduction to CO and Methanol over a Silicon Photocathode Functionalized with a Cobalt Phthalocyanine Molecular Catalyst.

We report a precious-metal-free molecular catalyst-based photocathode that is active for aqueous CO reduction to CO and methanol. The photoelectrode is composed of cobalt phthalocyanine molecules anchored on graphene oxide which is integrated via a (3-aminopropyl)triethoxysilane linker to p-type silicon protected by a thin film of titanium dioxide. The photocathode reduces CO to CO with high selectivity at potentials as mild as 0 V versus the reversible hydrogen electrode (vs RHE).

Monolithic and Single-Crystalline Aluminum-Silicon Heterostructures.

Overcoming the difficulty in the precise definition of the metal phase of metal-Si heterostructures is among the key prerequisites to enable reproducible next-generation nanoelectronic, optoelectronic, and quantum devices. Here, we report on the formation of monolithic Al-Si heterostructures obtained from both bottom-up and top-down fabricated Si nanostructures and Al contacts. This is enabled by a thermally induced Al-Si exchange reaction, which forms abrupt and void-free metal-semiconductor interfaces in contrast to their bulk counterparts.

Unveiling the complex configurational landscape of the intralayer cavities in a crystalline carbon nitride.

The in-depth understanding of the reported photoelectrochemical properties of the layered carbon nitride, poly(triazine imide)/LiCl (PTI/LiCl), has been limited by the apparent disorder of the Li/H atoms within its framework. To understand and resolve the current structural ambiguities, an optimized one-step flux synthesis (470 °C, 36 h, LiCl/KCl flux) was used to prepare PTI/LiCl and deuterated-PTI/LiCl in high purity. Its structure was characterized by a combination of neutron/X-ray diffraction and transmission electron microscopy.

Influence of Surface and Structural Variations in Donor-Acceptor-Donor Sensitizers on Photoelectrocatalytic Water Splitting.

Conjugated organic chromophores composed of linked donor (D) and acceptor (A) moieties have attracted considerable attention for photoelectrochemical applications. In this work, we compare the optoelectronic properties and photoelectrochemical performance of two D-A-D structural isomers with thiophene--carboxylic acid ( denotes 3 and 2 positions) derivatives and 2,1,3-benzothiadiazole as the D and A moieties, respectively. 5,5'-(Benzo[][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-3-carboxylic acid), , and 5,5'-(benzo[][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carboxylic acid), , were employed in the study to understand how structural isomers affect surface attachments within chromophore-catalyst assemblies and their influence on charge-transfer dynamics.

Electrostatic tip effects in scanning probe microscopy of nanostructures.

Electrical scanning probe microscopies (SPM) use ultrasharp metallic tips to obtain nanometer spatial resolution and are a key tool for characterizing nanoscale semiconducting materials and systems. However, these tips are not passive probes; their high work functions can induce local band bending whose effects depend sensitively on the local geometry and material properties and thus are inherently difficult to quantify. We use sequential finite element simulations to first explore the magnitude and spatial distribution of charge reorganization due to tip-induced band bending (TIBB) for planar and nanostructured geometries.

Remote nongenetic optical modulation of neuronal activity using fuzzy graphene.

The ability to modulate cellular electrophysiology is fundamental to the investigation of development, function, and disease. Currently, there is a need for remote, nongenetic, light-induced control of cellular activity in two-dimensional (2D) and three-dimensional (3D) platforms. Here, we report a breakthrough hybrid nanomaterial for remote, nongenetic, photothermal stimulation of 2D and 3D neural cellular systems.

Abrupt degenerately-doped silicon nanowire tunnel junctions.

We have confirmed the presence of narrow, degenerately-doped axial silicon nanowire (SiNW) p-n junctions via off-axis electron holography (EH). SiNWs were grown via the vapor-solid-liquid (VLS) mechanism using gold (Au) as the catalyst, silane (SiH), diborane (BH) and phosphine (PH) as the precursors, and hydrochloric acid (HCl) to stabilize the growth. Two types of growth were carried out, and in each case we explored growth with both n/p and p/n sequences.

Ratcheting quasi-ballistic electrons in silicon geometric diodes at room temperature.

Ratcheting effects play an important role in systems ranging from mechanical socket wrenches to biological motor proteins. The underlying principle is to convert a fluctuating, unbiased force into unidirectional motion. Here, we report the ratcheting of electrons at room temperature using a semiconductor nanowire with precisely engineered asymmetry.

Geometric Nanophotonics: Light Management in Single Nanowires through Morphology.

Comprehensive control of light-matter interactions at the nanoscale is increasingly important for the development of miniaturized light-based technologies that have applications ranging from information processing to sensing. Control of light in nanoscale structures-the realm of nanophotonics-requires precise control of geometry on a few-nanometer length scale. From a chemist's perspective, bottom-up growth of nanoscale materials from chemical precursors offers a unique opportunity to design structures atom-by-atom that exhibit desired properties.

Optical Bound States in the Continuum with Nanowire Geometric Superlattices.

Perfect trapping of light in a subwavelength cavity is a key goal in nanophotonics. Perfect trapping has been realized with optical bound states in the continuum (BIC) in waveguide arrays and photonic crystals; yet the formal requirement of infinite periodicity has limited the experimental realization to structures with macroscopic planar dimensions. We characterize BICs in a silicon nanowire (NW) geometric superlattice (GSL) that exhibits one-dimensional periodicity in a compact cylindrical geometry with a subwavelength diameter.

Solvent-Engineered Stress in Nanoscale Materials.

Nanoscale materials are frequently coated with surface stabilization layers during growth that prevent flocculation in solution and facilitate processing technologies such as ink-jet device printing. Here, we show that few-nanometer-thick stabilization layers typically used swell in the presence of certain solvents and impart significant stresses to the nanomaterial that remains even after the solvent has evaporated. Solvent swelling of the surface layer dramatically enhances nanomaterial-substrate adhesion via the collapse of the stabilization layer during solvent evaporation, preventing stress relaxation.

Interplay of Surface Recombination and Diode Geometry for the Performance of Axial p-i-n Nanowire Solar Cells.

Nanowires (NWs) with axial p-i-n junctions have been widely explored as microscopic diodes for optoelectronic and solar energy applications, and their performance is strongly influenced by charge recombination at the surface. We delineate how the photovoltaic performance of these diodes is dictated not only by the surface but also by the complex and seemingly counterintuitive interplay of diode geometry, that is, radius ( R) and intrinsic length ( L), with the surface recombination velocity ( S). An analytical model to describe these relationships is developed and compared to finite-element simulations, which verify the accuracy and limitations of the model.

Mie-coupled bound guided states in nanowire geometric superlattices.

All-optical operation holds promise as the future of computing technology, and key components include miniaturized waveguides (WGs) and couplers that control narrow bandwidths. Nanowires (NWs) offer an ideal platform for nanoscale WGs, but their utility has been limited by the lack of a comprehensive coupling scheme with band selectivity. Here, we introduce a NW geometric superlattice (GSL) that allows narrow-band guiding in Si NWs through coupling of a Mie resonance with a bound-guided state (BGS).

Enhancement of Light Absorption in Silicon Nanowire Photovoltaic Devices with Dielectric and Metallic Grating Structures.

We report the enhancement of light absorption in Si nanowire photovoltaic devices with one-dimensional dielectric or metallic gratings that are fabricated by a damage-free, precisely aligning, polymer-assisted transfer method. Incorporation of a SiN grating with a Si nanowire effectively enhances the photocurrents for transverse-electric polarized light. The wavelength at which a maximum photocurrent is generated is readily tuned by adjusting the grating pitch.