Toward Exotic Layered Materials: 2D Cuprous Iodide.

Heterostructures composed of 2D materials are already opening many new possibilities in such fields of technology as electronics and magnonics, but far more could be achieved if the number and diversity of 2D materials were increased. So far, only a few dozen 2D crystals have been extracted from materials that exhibit a layered phase in ambient conditions, omitting entirely the large number of layered materials that may exist at other temperatures and pressures. This work demonstrates how such structures can be stabilized in 2D van der Waals (vdw) stacks under room temperature via growing them directly in graphene encapsulation by using graphene oxide as the template material. Specifically, an ambient stable 2D structure of copper and iodine, a material that normally only occurs in layered form at elevated temperatures between 645 and 675 K, is produced. The results establish a simple route to the production of more exotic phases of materials that would otherwise be difficult or impossible to stabilize for experiments in ambient.

Atom-by-atom chemical identification from scanning transmission electron microscopy images in presence of noise and residual aberrations.

The simple dependence of the intensity in annular dark field scanning transmission electron microscopy images on the atomic number provides (to some extent) chemical information about the sample, and even allows an elemental identification in the case of light-element single-layer samples. However, the intensity of individual atoms and atomic columns is affected by residual aberrations and the confidence of an identification is limited by the available signal to noise. Here, we show that matching a simulation to an experimental image by iterative optimization provides a reliable analysis of atomic intensities even in presence of residual non-round aberrations. We compare our new method with other established approaches demonstrating its high reliability for images recorded at limited dose and with different aberrations. This is of particular relevance for analyzing moderately beam-sensitive materials, such as most 2D materials, where the limited sample stability often makes it difficult to obtain spectroscopic information at atomic resolution.

Ni-mediated reactions in nanocrystalline diamond on Si substrates: the role of the oxide barrier.

Nanocrystalline diamond (NCD) films grown on Si substrates by microwave plasma enhanced chemical vapor deposition (MWPECVD) were subjected to Ni-mediated graphitization to cover them with a conductive layer. Results of transmission electron microscopy including electron energy-loss spectroscopy of cross-sectional samples demonstrate that the oxide layer on Si substrates (∼5 nm native SiO2) has been damaged by microwave plasma during the early stage of NCD growth. During the heat treatment for graphitizing the NCD layer, the permeability or absence of the oxide barrier allow Ni nanoparticles to diffuse into the Si substrate and cause additional solid-state reactions producing pyramidal crystals of NiSi2 and SiC nanocrystals. The latter are found impinged into the NiSi2 pyramids but only when the interfacial oxide layer is absent, replaced by amorphous SiC. The complex phase morphology of the samples is also reflected in the temperature dependence of electrical conductivity, where multiple pathways of the electronic transport dominate in different temperature regions. We present models explaining the observed cascade of solid-state reactions and resulting electronic transport properties of such heterostructures.

Direct imaging of light-element impurities in graphene reveals triple-coordinated oxygen.

Along with hydrogen, carbon, nitrogen and oxygen are the arguably most important elements for organic chemistry. Due to their rich variety of possible bonding configurations, they can form a staggering number of compounds. Here, we present a detailed analysis of nitrogen and oxygen bonding configurations in a defective carbon (graphene) lattice. Using aberration-corrected scanning transmission electron microscopy and single-atom electron energy loss spectroscopy, we directly imaged oxygen atoms in graphene oxide, as well as nitrogen atoms implanted into graphene. The collected data allows us to compare nitrogen and oxygen bonding configurations, showing clear differences between the two elements. As expected, nitrogen forms either two or three bonds with neighboring carbon atoms, with three bonds being the preferred configuration. Oxygen, by contrast, tends to bind with only two carbon atoms. Remarkably, however, triple-coordinated oxygen with three carbon neighbors is also observed, a configuration that is exceedingly rare in organic compounds.

Enhanced Tunneling in a Hybrid of Single-Walled Carbon Nanotubes and Graphene.

Transparent and conductive films (TCFs) are of great technological importance. Their high transmittance, electrical conductivity, and mechanical strength make single-walled carbon nanotubes (SWCNTs) a good candidate for the raw material for TCFs. Despite the ballistic transport in individual SWCNTs, electrical conductivity of SWCNT networks is limited by low efficiency of charge tunneling between the tube elements. Here, we demonstrate that the nanotube network sheet resistance at high optical transmittance is decreased by more than 50% when fabricated on graphene. This is a comparable improvement as that obtained through gold chloride (AuCl3) doping. However, while Raman spectroscopy reveals substantial changes in spectral features of AuCl3 doped nanotubes, this does not occur with graphene. Instead, temperature-dependent transport measurements indicate that a graphene substrate reduces the tunneling barrier heights, while its parallel conductivity contribution is almost negligible. Finally, we show that combining the graphene substrate and AuCl3 doping, brings the SWCNT thin film sheet resistance down to 36 Ω/□.

Covalent Diamond-Graphite Bonding: Mechanism of Catalytic Transformation.

Aberration-corrected transmission electron microscopy of the atomic structure of diamond-graphite interface after Ni-induced catalytic transformation reveals graphitic planes bound covalently to the diamond in the upright orientation. The covalent attachment, together with a significant volume expansion of graphite transformed from diamond, gives rise to uniaxial stress that is released through plastic deformation. We propose a comprehensive model explaining the Ni-mediated transformation of diamond to graphite and covalent bonding at the interface as well as the mechanism of relaxation of uniaxial stress. We also explain the mechanism of electrical transport through the graphitized surface of diamond. The result may thus provide a foundation for the catalytically driven formation of graphene-diamond nanodevices.

Tuning the orientation of few-layer MoS2 films using one-zone sulfurization.

Few-layer MoS2 films are promising candidates for applications in numerous areas, such as photovoltaics, photocatalysis, nanotribology, lithium batteries, hydro-desulfurization catalysis and dry lubricants, especially due to their distinctive electronic, optical, and catalytic properties. In general, two alignments of MoS2 layers are possible - the horizontal and the vertical one, having different physicochemical properties. Layers of both orientations are conventionally fabricated by a sulfurization of pre-deposited Mo films. So far, the Mo thickness was considered as a critical parameter influencing the final orientation of MoS2 layers with horizontally and vertically aligned MoS2 grown from thin (1 nm) and thick (3 nm) Mo films, respectively. Here, we present a fabrication protocol enabling the growth of horizontally or vertically aligned few-layer MoS2 films utilizing the same Mo thickness of 3 nm. We show that the sulfur vapor is another parameter influencing the growth mechanism, where a sulfurization with higher sulfur vapor pressure leads to vertical MoS2 layers and slow sulfur evaporation results in horizontally aligned layers for a thicker Mo starting layer.

Inhibition of E. coli Growth by Nanodiamond and Graphene Oxide Enhanced by Luria-Bertani Medium.

Nanodiamonds (NDs) and graphene oxide (GO) are modern carbon-based nanomaterials with promising features for the inhibition of microorganism growth ability. Here we compare the effects of nanodiamond and graphene oxide in both annealed (oxidized) and reduced (hydrogenated) forms in two types of cultivation media-Luria-Bertani (LB) and Mueller-Hinton (MH) broths. The comparison shows that the number of colony forming unit (CFU) of Escherichia coli is significantly lowered (45%) by all the nanomaterials in LB medium for at least 24 h against control. On the contrary, a significant long-term inhibition of E. coli growth (by 45%) in the MH medium is provided only by hydrogenated NDs terminated with C-HX groups. The use of salty agars did not enhance the inhibition effects of nanomaterials used, i.e. disruption of bacterial membrane or differences in ionic concentrations do not play any role in bactericidal effects of nanomaterials used. The specific role of the ND and GO on the enhancement of the oxidative stress of bacteria or possible wrapping bacteria by GO nanosheets, therefore isolating them from both the environment and nutrition was suggested. Analyses by infrared spectroscopy, photoelectron spectroscopy, scanning electron microscopy and dynamic light scattering corroborate these conclusions.

Computational insights and the observation of SiC nanograin assembly: towards 2D silicon carbide.

While an increasing number of two-dimensional (2D) materials, including graphene and silicene, have already been realized, others have only been predicted. An interesting example is the two-dimensional form of silicon carbide (2D-SiC). Here, we present an observation of atomically thin and hexagonally bonded nanosized grains of SiC assembling temporarily in graphene oxide pores during an atomic resolution scanning transmission electron microscopy experiment. Even though these small grains do not fully represent the bulk crystal, simulations indicate that their electronic structure already approaches that of 2D-SiC. This is predicted to be flat, but some doubts have remained regarding the preference of Si for sp 3 hybridization. Exploring a number of corrugated morphologies, we find completely flat 2D-SiC to have the lowest energy. We further compute its phonon dispersion, with a Raman-active transverse optical mode, and estimate the core level binding energies. Finally, we study the chemical reactivity of 2D-SiC, suggesting it is like silicene unstable against molecular absorption or interlayer linking. Nonetheless, it can form stable van der Waals-bonded bilayers with either graphene or hexagonal boron nitride, promising to further enrich the family of two-dimensional materials once bulk synthesis is achieved.

Growth, structure and stability of sputter-deposited MoS2 thin films.

Molybdenum disulphide (MoS2) thin films have received increasing interest as device-active layers in low-dimensional electronics and also as novel catalysts in electrochemical processes such as the hydrogen evolution reaction (HER) in electrochemical water splitting. For both types of applications, industrially scalable fabrication methods with good control over the MoS2 film properties are crucial. Here, we investigate scalable physical vapour deposition (PVD) of MoS2 films by magnetron sputtering. MoS2 films with thicknesses from ≈10 to ≈1000 nm were deposited on SiO2/Si and reticulated vitreous carbon (RVC) substrates. Samples deposited at room temperature (RT) and at 400 °C were compared. The deposited MoS2 was characterized by macro- and microscopic X-ray, electron beam and light scattering, scanning and spectroscopic methods as well as electrical device characterization. We find that room-temperature-deposited MoS2 films are amorphous, of smooth surface morphology and easily degraded upon moderate laser-induced annealing in ambient conditions. In contrast, films deposited at 400 °C are nano-crystalline, show a nano-grained surface morphology and are comparatively stable against laser-induced degradation. Interestingly, results from electrical transport measurements indicate an unexpected metallic-like conduction character of the studied PVD MoS2 films, independent of deposition temperature. Possible reasons for these unusual electrical properties of our PVD MoS2 thin films are discussed. A potential application for such conductive nanostructured MoS2 films could be as catalytically active electrodes in (photo-)electrocatalysis and initial electrochemical measurements suggest directions for future work on our PVD MoS2 films.

High-yield fabrication and properties of 1.4 nm nanodiamonds with narrow size distribution.

Detonation nanodiamonds (DNDs) with a typical size of 5 nm have attracted broad interest in science and technology. Further size reduction of DNDs would bring these nanoparticles to the molecular-size level and open new prospects for research and applications in various fields, ranging from quantum physics to biomedicine. Here we show a controllable size reduction of the DND mean size down to 1.4 nm without significant particle loss and with additional disintegration of DND core agglutinates by air annealing, leading to a significantly narrowed size distribution (±0.7 nm). This process is scalable to large quantities. Such molecular-sized DNDs keep their diamond structure and characteristic DND features as shown by Raman spectroscopy, infrared spectroscopy, STEM and EELS. The size of 1 nm is identified as a limit, below which the DNDs become amorphous.

Vibrational Properties of a Two-Dimensional Silica Kagome Lattice.

Kagome lattices are structures possessing fascinating magnetic and vibrational properties, but in spite of a large body of theoretical work, experimental realizations and investigations of their dynamics are scarce. Using a combination of Raman spectroscopy and density functional theory calculations, we study the vibrational properties of two-dimensional silica (2D-SiO2), which has a kagome lattice structure. We identify the signatures of crystalline and amorphous 2D-SiO2 structures in Raman spectra and show that, at finite temperatures, the stability of 2D-SiO2 lattice is strongly influenced by phonon-phonon interaction. Our results not only provide insights into the vibrational properties of 2D-SiO2 and kagome lattices in general but also suggest a quick nondestructive method to detect 2D-SiO2.

Size and Purity Control of HPHT Nanodiamonds down to 1 nm.

High-pressure high-temperature (HPHT) nanodiamonds originate from grinding of diamond microcrystals obtained by HPHT synthesis. Here we report on a simple two-step approach to obtain as small as 1.1 nm HPHT nanodiamonds of excellent purity and crystallinity, which are among the smallest artificially prepared nanodiamonds ever shown and characterized. Moreover we provide experimental evidence of diamond stability down to 1 nm. Controlled annealing at 450 °C in air leads to efficient purification from the nondiamond carbon (shells and dots), as evidenced by X-ray photoelectron spectroscopy, Raman spectroscopy, photoluminescence spectroscopy, and scanning transmission electron microscopy. Annealing at 500 °C promotes, besides of purification, also size reduction of nanodiamonds down to ∼1 nm. Comparably short (1 h) centrifugation of the nanodiamonds aqueous colloidal solution ensures separation of the sub-10 nm fraction. Calculations show that an asymmetry of Raman diamond peak of sub-10 nm HPHT nanodiamonds can be well explained by modified phonon confinement model when the actual particle size distribution is taken into account. In contrast, larger Raman peak asymmetry commonly observed in Raman spectra of detonation nanodiamonds is mainly attributed to defects rather than to the phonon confinement. Thus, the obtained characteristics reflect high material quality including nanoscale effects in sub-10 nm HPHT nanodiamonds prepared by the presented method.

Fractional Quantum Hall States in Bilayer Graphene Probed by Transconductance Fluctuations.

We have investigated fractional quantum Hall (QH) states in Bernal-stacked bilayer graphene using transconductance fluctuation measurements. A variety of odd-denominator fractional QH states with νQH → νQH + 2 symmetry, as previously reported, are observed. However, surprising is that also particle-hole symmetric states are clearly resolved in the same measurement set. We attribute their emergence to the reversal of orbital states in the octet level scheme induced by a strong local charge imbalance, which can be captured by the transconductance fluctuations. Also the even-denominator fractional QH state at filling -1/2 is observed. However, contrary to a previous study on a suspended graphene layer [ Ki et al. Nano Lett. 2014, 14 , 2135 ], the particle-hole symmetric state at filling 1/2 is detected as well. These observations suggest that the stability of both odd and even denominator fractional QH states is very sensitive to local transverse electric fields in bilayer graphene.

Dimensional crossover in the quantum transport behaviour of the natural topological insulator Aleksite.

Three-dimensional topological insulators comprise topologically protected surface states displaying massless, Dirac-like linear dispersion with spin-momentum locking. Electrical conduction through such surface states has been documented to manifest itself in a two-dimensional character of the angle-dependent magnetotransport behavior. Here, we explore the size-dependent electronic properties of nanostructures made of the lead-containing mineral Aleksite, a naturally occurring topological insulator. Compared to its sister compound Kawazulite, a member of the well-studied Tetradymite crystal class, the crystal structure of Aleksite is distinguished by its lack of any counterpart within the group of synthetic topological insulators. Low temperature Hall measurements on thin Aleksite nanosheets reveal a significant carrier mobility on the order of 1000 cm(2)/(Vs), and a high carrier density of n = 3.9 × 10(25) m(-3). Importantly, for Aleksite nanoribbons with a width below 150 nm, a 1D weak antilocalization effect along with 1D universal conductance fluctuations emerges, which transforms into 2D behavior for larger ribbon widths.

Defects in bilayer silica and graphene: common trends in diverse hexagonal two-dimensional systems.

By combining first-principles and classical force field calculations with aberration-corrected high-resolution transmission electron microscopy experiments, we study the morphology and energetics of point and extended defects in hexagonal bilayer silica and make comparison to graphene, another two-dimensional (2D) system with hexagonal symmetry. We show that the motifs of isolated point defects in these 2D structures with otherwise very different properties are similar, and include Stone-Wales-type defects formed by structural unit rotations, flower defects and reconstructed double vacancies. The morphology and energetics of extended defects, such as grain boundaries have much in common as well. As both sp(2)-hybridised carbon and bilayer silica can also form amorphous structures, our results indicate that the morphology of imperfect 2D honeycomb lattices is largely governed by the underlying symmetry of the lattice.

Probing from both sides: reshaping the graphene landscape via face-to-face dual-probe microscopy.

In two-dimensional samples, all atoms are at the surface and thereby exposed for probing and manipulation by physical or chemical means from both sides. Here, we show that we can access the same point on both surfaces of a few-layer graphene membrane simultaneously, using a dual-probe scanning tunneling microscopy (STM) setup. At the closest point, the two probes are separated only by the thickness of the graphene membrane. This allows us for the first time to directly measure the deformations induced by one STM probe on a free-standing membrane with an independent second probe. We reveal different regimes of stability of few-layer graphene and show how the STM probes can be used as tools to shape the membrane in a controlled manner. Our work opens new avenues for the study of mechanical and electronic properties of two-dimensional materials.

Atomistic description of electron beam damage in nitrogen-doped graphene and single-walled carbon nanotubes.

By combining ab initio simulations with state-of-the-art electron microscopy and electron energy loss spectroscopy, we study the mechanism of electron beam damage in nitrogen-doped graphene and carbon nanotubes. Our results show that the incorporation of nitrogen atoms results in noticeable knock-on damage in these structures already at an acceleration voltage of 80 kV, at which essentially no damage is created in pristine structures at corresponding doses. Contrary to an early estimate predicting rapid destruction via sputtering of the nitrogen atoms, in the case of substitutional doping, damage is initiated by displacement of carbon atoms neighboring the nitrogen dopant, leading to the conversion of substitutional dopant sites into pyridinic ones. Although such events are relatively rare at 80 kV, they become significant at higher voltages typically used in electron energy loss spectroscopy studies. Correspondingly, we measured an energy loss spectrum time series at 100 kV that provides direct evidence for such conversions in nitrogen-doped single-walled carbon nanotubes, in excellent agreement with our theoretical prediction. Besides providing an improved understanding of the irradiation stability of these structures, we show that structural changes cannot be neglected in their characterization employing high-energy electrons.

Transconductance fluctuations as a probe for interaction-induced quantum Hall states in graphene.

Transport measurements normally provide a macroscopic, averaged view of the sample so that disorder prevents the observation of fragile interaction-induced states. Here, we demonstrate that transconductance fluctuations in a graphene field effect transistor reflect charge localization phenomena on the nanometer scale due to the formation of a dot network which forms near incompressible quantum states. These fluctuations give access to fragile broken symmetry and fractional quantum Hall states even though these states remain hidden in conventional magnetotransport quantities.

Accurate measurement of electron beam induced displacement cross sections for single-layer graphene.

We present an accurate measurement and a quantitative analysis of electron-beam-induced displacements of carbon atoms in single-layer graphene. We directly measure the atomic displacement ("knock-on") cross section by counting the lost atoms as a function of the electron-beam energy and applied dose. Further, we separate knock-on damage (originating from the collision of the beam electrons with the nucleus of the target atom) from other radiation damage mechanisms (e.g., ionization damage or chemical etching) by the comparison of ordinary (12C) and heavy (13C) graphene. Our analysis shows that a static lattice approximation is not sufficient to describe knock-on damage in this material, while a very good agreement between calculated and experimental cross sections is obtained if lattice vibrations are taken into account.