Duncan T. L. Alexander

Light trapping in solar cells: can periodic beat random?

Theory predicts that periodic photonic nanostructures should outperform their random counterparts in trapping light in solar cells. However, the current certified world-record conversion efficiency for amorphous silicon thin-film solar cells, which strongly rely on light trapping, was achieved on the random pyramidal morphology of transparent zinc oxide electrodes. Based on insights from waveguide theory, we develop tailored periodic arrays of nanocavities on glass fabricated by nanosphere lithography, which enable a cell with a remarkable short-circuit current density of 17.1 mA/cm(2) and a high initial efficiency of 10.9%. A direct comparison with a cell deposited on the random pyramidal morphology of state-of-the-art zinc oxide electrodes, replicated onto glass using nanoimprint lithography, demonstrates unambiguously that periodic structures rival random textures.

Ripples and Layers in Ultrathin MoS2 Membranes

Single-layer molybdenum disulfide (MoS2) is a newly emerging two-dimensional semiconductor with a potentially wide range of applications in the fields of nanoelectronics and energy harvesting. The fact that it can be exfoliated down to single-layer thickness makes MoS2 interesting both for practical applications and for fundamental research, where the structure and crystalline order of ultrathin MoS2 will have a strong influence on electronic, mechanical, and other properties. Here, we report on the transmission electron microscopy study of suspended single- and few-layer MoS2 membranes with thicknesses previously determined using both optical identification and atomic force microscopy. Electron microscopy shows that monolayer MoS2 displays long-range crystalline order, although surface roughening has been observed with ripples which can reach 1 nm in height, just as in the case of graphene, implying that similar mechanisms are responsible for the stability of both two-dimensional materials. The observed ripples could explain the degradation of mobility in MoS2 due to exfoliation. We also find that symmetry breaking due to the reduction of the number of layers results in distinctive features in electron-beam diffraction patterns of single- and multilayer MoS2, which could be used as a method for identifying single layers using only electron microscopy. The isolation of suspended single-layer MoS2 membranes will improve our understanding of two-dimensional systems, their stability, and the interplay between their structures, morphologies, and electrical and mechanical properties.

Silicon Filaments in Silicon Oxide for Next-Generation Photovoltaics

Nanometer wide silicon filaments embedded in an amorphous silicon oxide matrix are grown at low temperatures over a large area. The optical and electrical properties of these mixed-phase nanomaterials can be tuned independently, allowing for advanced light management in high efficiency thin-film silicon solar cells and for band-gap tuning via quantum confinement in third-generation photovoltaics.

Highly Dynamic Cellular-Level Response of Symbiotic Coral to a Sudden Increase in Environmental Nitrogen

ABSTRACT Metabolic interactions with endosymbiotic photosynthetic dinoflagellate Symbiodinium spp. are fundamental to reef-building corals (Scleractinia) thriving in nutrient-poor tropical seas. Yet, detailed understanding at the single-cell level of nutrient assimilation, translocation, and utilization within this fundamental symbiosis is lacking. Using pulse-chase 15N labeling and quantitative ion microprobe isotopic imaging (NanoSIMS; nanoscale secondary-ion mass spectrometry), we visualized these dynamic processes in tissues of the symbiotic coral Pocillopora damicornis at the subcellular level. Assimilation of ammonium, nitrate, and aspartic acid resulted in rapid incorporation of nitrogen into uric acid crystals (after ~45 min), forming temporary N storage sites within the dinoflagellate endosymbionts. Subsequent intracellular remobilization of this metabolite was accompanied by translocation of nitrogenous compounds to the coral host, starting at ~6 h. Within the coral tissue, nitrogen is utilized in specific cellular compartments in all four epithelia, including mucus chambers, Golgi bodies, and vesicles in calicoblastic cells. Our study shows how nitrogen-limited symbiotic corals take advantage of sudden changes in nitrogen availability; this opens new perspectives for functional studies of nutrient storage and remobilization in microbial symbioses in changing reef environments. IMPORTANCE The methodology applied, combining transmission electron microscopy with nanoscale secondary-ion mass spectrometry (NanoSIMS) imaging of coral tissue labeled with stable isotope tracers, allows quantification and submicrometric localization of metabolic fluxes in an intact symbiosis. This study opens the way for investigations of physiological adaptations of symbiotic systems to nutrient availability and for increasing knowledge of global nitrogen and carbon biogeochemical cycling. The methodology applied, combining transmission electron microscopy with nanoscale secondary-ion mass spectrometry (NanoSIMS) imaging of coral tissue labeled with stable isotope tracers, allows quantification and submicrometric localization of metabolic fluxes in an intact symbiosis. This study opens the way for investigations of physiological adaptations of symbiotic systems to nutrient availability and for increasing knowledge of global nitrogen and carbon biogeochemical cycling.

Electrochemical Reaction in Single Layer MoS2: Nanopores Opened Atom by Atom

Ultrathin nanopore membranes based on 2D materials have demonstrated ultimate resolution toward DNA sequencing. Among them, molybdenum disulfide (MoS2) shows long-term stability as well as superior sensitivity enabling high throughput performance. The traditional method of fabricating nanopores with nanometer precision is based on the use of focused electron beams in transmission electron microscope (TEM). This nanopore fabrication process is time-consuming, expensive, not scalable, and hard to control below 1 nm. Here, we exploited the electrochemical activity of MoS2 and developed a convenient and scalable method to controllably make nanopores in single-layer MoS2 with subnanometer precision using electrochemical reaction (ECR). The electrochemical reaction on the surface of single-layer MoS2 is initiated at the location of defects or single atom vacancy, followed by the successive removals of individual atoms or unit cells from single-layer MoS2 lattice and finally formation of a nanopore. Step-like features in the ionic current through the growing nanopore provide direct feedback on the nanopore size inferred from a widely used conductance vs pore size model. Furthermore, DNA translocations can be detected in situ when as-fabricated MoS2 nanopores are used. The atomic resolution and accessibility of this approach paves the way for mass production of nanopores in 2D membranes for potential solid-state nanopore sequencing.

Amorphous/crystalline silicon interface defects induced by hydrogen plasma treatments

Excellent amorphous/crystalline silicon interface passivation is of extreme importance for high-efficiency silicon heterojunction solar cells. This can be obtained by inserting hydrogen-plasma treatments during deposition of the amorphous silicon passivation layers. Prolonged hydrogen-plasmas lead to film etching. We report on the defect creation induced by such treatments: A severe drop in interface-passivation quality is observed when films are etched to a thickness of less than 8 nm. Detailed characterization shows that this decay is due to persistent defects created at the crystalline silicon surface. Pristine interfaces are preserved when the post-etching film thickness exceeds 8 nm, yielding high quality interface passivation.

Nanoscale topographical control of capillary assembly of nanoparticles

Predetermined and selective placement of nanoparticles onto large-area substrates with nanometre-scale precision is essential to harness the unique properties of nanoparticle assemblies, in particular for functional optical and electro-optical nanodevices. Unfortunately, such high spatial organization is currently beyond the reach of top-down nanofabrication techniques alone. Here, we demonstrate that topographic features comprising lithographed funnelled traps and auxiliary sidewalls on a solid substrate can deterministically direct the capillary assembly of Au nanorods to attain simultaneous control of position, orientation and interparticle distance at the nanometre level. We report up to 100% assembly yield over centimetre-scale substrates. We achieve this by optimizing the three sequential stages of capillary nanoparticle assembly: insertion of nanorods into the traps, resilience against the receding suspension front and drying of the residual solvent. Finally, using electron energy-loss spectroscopy we characterize the spectral response and near-field properties of spatially programmable Au nanorod dimers, highlighting the opportunities for precise tunability of the plasmonic modes in larger assemblies.

CsPbBr3 QD/AlOx Inorganic Nanocomposites with Exceptional Stability in Water, Light, and Heat

Herein, the assembly of CsPbBr3 QD/AlOx inorganic nanocomposites, by using atomic layer deposition (ALD) for the growth of the amorphous alumina matrix (AlOx ), is described as a novel protection scheme for such QDs. The nucleation and growth of AlOx on the QD surface was thoroughly investigated by miscellaneous techniques, which highlighted the importance of the interaction between the ALD precursors and the QD surface to uniformly coat the QDs while preserving the optoelectronic properties. These nanocomposites show exceptional stability towards exposure to air (for at least 45 days), irradiation under simulated solar spectrum conditions (for at least 8 h), and heat (up to 200 °C in air), and finally upon immersion in water. This method was extended to the assembly of CsPbBrx I3-x QD/AlOx and CsPbI3 QD/AlOx nanocomposites, which were more stable than the pristine QD films.

Large-area MoS2 grown using H2S as the sulphur source

We report on the growth of molybdenum disulphide (MoS2) using H2S as a gas-phase sulfur precursor that allows controlling the domain growth direction of domains in both vertical (perpendicular to the substrate plane) and horizontal (within the substrate plane), depending on the H2S:H2 ratio in the reaction gas mixture and temperature at which they are introduced during growth. Optical and atomic force microscopy measurements on horizontal MoS2 demonstrate the formation of monolayer triangular-shape domains that merge into a continuous film. Scanning transmission electron microscopy of monolayer MoS2 shows a regular atomic structure with a hexagonal symmetry. Raman and photoluminescence spectra confirm the monolayer thickness of the material. Field-effect transistors fabricated on MoS2 domains that are transferred onto Si/SiO2 substrates show a mobility similar to previously reported exfoliated and chemical vapor deposition-grown materials.

In-Plane Plasmonic Antenna Arrays with Surface Nanogaps for Giant Fluorescence Enhancement

Optical nanoantennas have a great potential for enhancing light-matter interactions at the nanometer scale, yet fabrication accuracy and lack of scalability currently limit ultimate antenna performance and applications. In most designs, the region of maximum field localization and enhancement (i.e., hotspot) is not readily accessible to the sample because it is buried into the nanostructure. Moreover, current large-scale fabrication techniques lack reproducible geometrical control below 20 nm. Here, we describe a new nanofabrication technique that applies planarization, etch back, and template stripping to expose the excitation hotspot at the surface, providing a major improvement over conventional electron beam lithography methods. We present large flat surface arrays of in-plane nanoantennas, featuring gaps as small as 10 nm with sharp edges, excellent reproducibility and full surface accessibility of the hotspot confined region. The novel fabrication approach drastically improves the optical performance of plasmonic nanoantennas to yield giant fluorescence enhancement factors up to 104-105 times, together with nanoscale detection volumes in the 20 zL range. The method is fully scalable and adaptable to a wide range of antenna designs. We foresee broad applications by the use of these in-plane antenna geometries ranging from large-scale ultrasensitive sensor chips to microfluidics and live cell membrane investigations.