Gerardo Algara-Siller

Selective Sputtering and Atomic Resolution Imaging of Atomically Thin Boron Nitride Membranes

We report on the preparation, atomic resolution imaging, and element selective damage mechanism in atomically thin boron nitride membranes. Flakes of less than 10 layers are prepared by mechanical cleavage and are thinned down to single layers in a high-energy electron beam. At our beam energies, we observe a highly selective sputtering of only one of the elements and predominantly at the exit surface of the specimen, and then subsequent removal of atoms next to a defect. Triangle-shaped holes appear in accordance with the crystallographic orientation of each layer. Defects are compared to those observed in graphene membranes. The observation of clean single-layer membranes shows that hexagonal boron nitride is a further material (in addition to graphene) that can exist in a quasi-two-dimensional allotrope without the need for a substrate.

From graphene constrictions to single carbon chains

We present an atomic-resolution observation and analysis of graphene constrictions and ribbons with sub-nanometer width. Graphene membranes are studied by imaging side spherical aberration-corrected transmission electron microscopy at 80?kV. Holes are formed in the honeycomb-like structure due to radiation damage. As the holes grow and two holes approach each other, the hexagonal structure that lies between them narrows down. Transitions and deviations from the hexagonal structure in this graphene ribbon occur as its width shrinks below one nanometer. Some reconstructions, involving more pentagons and heptagons than hexagons, turn out to be surprisingly stable. Finally, single carbon atom chain bridges between graphene contacts are observed. The dynamics are observed in real time at atomic resolution with enough sensitivity to detect every carbon atom that remains stable for a sufficient amount of time. The carbon chains appear reproducibly and in various configurations from graphene bridges, between adsorbates, or at open edges and seem to represent one of the most stable configurations that a few atomic carbon system accommodates in the presence of continuous energy input from the electron beam.

Triazine‐Based Graphitic Carbon Nitride: a Two‐Dimensional Semiconductor

Graphitic carbon nitride has been predicted to be structurally analogous to carbon-only graphite, yet with an inherent bandgap. We have grown, for the first time, macroscopically large crystalline thin films of triazine-based, graphitic carbon nitride (TGCN) using an ionothermal, interfacial reaction starting with the abundant monomer dicyandiamide. The films consist of stacked, two-dimensional (2D) crystals between a few and several hundreds of atomic layers in thickness. Scanning force and transmission electron microscopy show long-range, in-plane order, while optical spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations corroborate a direct bandgap between 1.6 and 2.0 eV. Thus TGCN is of interest for electronic devices, such as field-effect transistors and light-emitting diodes.

Experimental analysis of charge redistribution due to chemical bonding by high-resolution transmission electron microscopy

The electronic charge density distribution or the electrostatic atomic potential of a solid or molecule contains information not only on the atomic structure, but also on the electronic properties, such as the nature of the chemical bonds or the degree of ionization of atoms. However, the redistribution of charge due to chemical bonding is small compared with the total charge density, and therefore difficult to measure. Here, we demonstrate an experimental analysis of charge redistribution due to chemical bonding by means of high-resolution transmission electron microscopy (HRTEM). We analyse charge transfer on the single-atom level for nitrogen-substitution point defects in graphene, and confirm the ionicity of single-layer hexagonal boron nitride. Our combination of HRTEM experiments and first-principles electronic structure calculations opens a new way to investigate electronic configurations of point defects, other non-periodic arrangements or nanoscale objects that cannot be studied by an electron or X-ray diffraction analysis.

Detection of a few metallo-protein molecules using color centers in nanodiamonds.

Nanometer-sized diamonds containing nitrogen-vacancy defect centers (NV) are promising nanosensors in biological environments due to their biocompatibility, bright fluorescence, and high magnetic sensitivity at ambient conditions. Here we report on the detection of ferritin molecules using magnetic noise induced by the inner paramagnetic iron as a contrast mechanism. We observe a significant reduction of both coherence and relaxation time due to the presence of ferritin on the surface of nanodiamonds. Our theoretical model is in excellent agreement with the experimental data and establishes this method as a novel sensing technology for proteins.

The pristine atomic structure of MoS2 monolayer protected from electron radiation damage by graphene

Materials can, in principle, be imaged at the level of individual atoms with aberration-corrected transmission electron microscopy. However, such resolution can be attained only with very high electron doses. Consequently, radiation damage is often the limiting factor when characterizing sensitive materials. Here, we demonstrate a simple and an effective method to increase the electron radiation tolerance of materials by using graphene as protective coating. This leads to an improvement of three orders of magnitude in the radiation tolerance of monolayer MoS2. Further on, we construct samples in different heterostructure configurations to separate the contributions of different radiation damage mechanisms.

Dry-cleaning of graphene

Studies of the structural and electronic properties of graphene in its pristine state are hindered by hydrocarbon contamination on the surfaces. Also, in many applications, contamination reduces the performance of graphene. Contamination is introduced during sample preparation and is adsorbed also directly from air. Here, we report on the development of a simple dry-cleaning method for producing large atomically clean areas in free-standing graphene. The cleanness of graphene is proven using aberration-corrected high-resolution transmission electron microscopy and electron spectroscopy.

A quantum dot photoswitch for DNA detection, gene transfection, and live-cell imaging.

Quantum dots (QDs) coated with an albumin-derived copolymer shell exhibit significant photoresponsiveness to DNA loading and have great potential for investigating gene delivery processes. The QDs reported herein are positively charged, have attractive optical properties, and are noncytotoxic and notably stable in live cells. Their complex formation with plasmid DNA leads to proportionally decreased photoluminescence and efficient gene transfection is observed. Therefore, they are suitable for live-cell bioimaging and mechanistic studies of nonviral gene delivery. Fluorescence correlation spectroscopy is applied for the first time to investigate individual QDs diffusing in large endosomes inside living cells, and serves as a valuable tool to study the physical properties of QDs inside live cells. The data obtained in this study strongly support the notable stability of these QDs, even in cell endosomes.

Experimental Observation of Boron-Nitride Chains

We report the formation and characterization of boron nitride atomic chains. The chains were made from hexagonal boron nitride sheets using the electron beam inside a transmission electron microscope. We find that the stability and lifetime of the chains are significantly improved when they are supported by another boron nitride layer. With the help of first-principles calculations, we prove the heteroatomic structure of the chains and determine their mechanical and electronic properties. Our study completes the analogy between various boron nitride and carbon polymorphs, in accordance with earlier theoretical predictions.

Twisted Bi‐Layer Graphene: Microscopic Rainbows

Blue, pink, and yellow colorations appear from twisted bi-layer graphene (tBLG) when transferred to a SiO2 /Si substrate (SiO2 = 100 nm-thick). Raman and electron microscope studies reveal that these colorations appear for twist angles in the 9-15° range. Optical contrast simulations confirm that the observed colorations are related to the angle-dependent electronic properties of tBLG combined with the reflection that results from the layered structure tBLG/100 nm-thick SiO2 /Si.