Graphene is one of the most promising 2D materials for various applications due to its unique electronic properties and high thermal stability. In previous studies, it was shown that when graphene is deposited onto some transition metal substrates, small molecules, such as O$_2$, intercalate between the graphene and the substrate and react to partially etch the graphene film when heated to desorb the intercalates. Here, carbon vacancy defects are intentionally formed on Gr/Ru(0001) and their effect on the intercalation of oxygen and etching of the graphene layer are investigated. 50 eV Ar$^+$ sputtering with a low fluence is used to create isolated single vacancy defects in the graphene overlayer and helium low energy ion scattering (LEIS) is employed for surface analysis. It is found that the defects both ease the intercalation of the oxygen molecules and improve the etching efficiency of the graphene during annealing.
We investigate nanoscale local anodic oxidation (LAO) on hydrogen-intercalated graphene grown by controlled sublimation of silicon carbide (SiC). Scanning probe microscopy (SPM) was used as a lithographic and characterization tool in order to investigate the local properties of the nanofabricated structures. The anomalous thickness observed after the graphene oxidation process is linked to the impact of LAO on the substrate. Micro-Raman spectroscopy was employed to demonstrate the presence of two oxidation regimes depending on the applied bias. We show that partial and total etching of monolay…
We study the formation of epitaxial graphene on Ru(0001) using fast x-ray photoelectron spectroscopy during the growth process. The assignment of different C 1s and Ru 3d core level components and their evolution during the growth process gives a detailed insight into the graphene formation and the strongly varying graphene-Ru interaction strength within the large moire unit cell. Subsequent intercalation of oxygen can be achieved at elevated temperature and the core level spectra show a conversion of the strongly corrugated to quasi free-standing graphene, characterised by a single narrow C 1…
Oxygen was electrochemically intercalated into Sr$_2$IrO$_4$ sintered samples, single crystals and a thin film. We estimate the diffusion length to a few $μ$m and the concentration of the intercalated oxygen to $δ$ $\simeq$ 0.01. The latter is thus much smaller than for the cuprate and nickelate parent compounds, for which $δ$ $>$ 0.1 is obtained, which could be a consequence of larger steric effects. The influence of the oxygen doping state on resistivity is small, indicating also a poor charge transfer to the conduction band. It is shown that electrochemical intercalation of oxygen may also …
O2-plamsa-based digital etching of Al0.25Ga0.75N with a 0.8 nm AlN spacer on GaN was investigated. At 40 W RF bias power and 40 sccm oxygen flow, the etch depth of Al0.25Ga0.75N was 5.7 nm per cycle. The 0.8 nm AlN spacer layer acted as an etch-stop layer in 3 cycles. The surface roughness improved to 0.33 nm after 7 digital etch cycles. Compared to the dry etch only approach, this technique causes less damages. It was shown to be effective in precisely controlling the AlGaN etch depth required for recessed-AlGaN HEMTs.
Patterned graphene shows substantial potential for applications in future molecular-scale integrated electronics. Environmental effects are a critical issue in a single layer material where every atom is on the surface. Especially intriguing is the variety of rich chemical interactions shown by molecular oxygen with aromatic molecules. We find that O2 etching kinetics vary strongly with the number of graphene layers in the sample. Three-layer-thick samples show etching similar to bulk natural graphite. Single-layer graphene reacts faster and shows random etch pits in contrast to natural graphi…
The chemical reactivity of graphene under ultraviolet (UV) light irradiation is investigated under positive and negative gate electric fields. Graphene edges are selectively etched when negative gate voltages are applied, while the reactivity is significantly suppressed for positive gate voltages. Oxygen adsorption onto graphene is significantly affected by the Fermi level of the final state achieved during previous electrical measurements. UV irradiation after negative-to-positive gate sweeps causes predominant oxygen desorption, while UV irradiation after gate sweeps in the opposite directio…
Aiming to improve fabrication protocols for boron nitride and graphene (h-BNG) lateral heterostructures, we studied the growth of h-BNG thin films on platinum and their behavior in an oxygen environment. We employed a surface science approach based on advanced spectroscopy and imaging techniques to investigate the evolution of surface stoichiometry and chemical intermediates at each reaction step. During oxygen exposure at increasing temperatures, we observed progressive and subsequent intercalation of oxygen, and selective etching of graphene accompanied by the oxidation of boron. Additionall…
We report a simple technique for the selective etching of bilayer and monolayer MoS$_2$. In this work, chosen regions of MoS$_2$ were activated for oxygen adsorption and reaction by the application of low doses of He$^+$ at 30 keV in a gas ion microscope. Raman spectroscopy, optical microscopy and scanning electron microscopy were used to characterize both the etched features and the remaining material. It has been found that by using a pre-treatment to introduce defects, MoS$_2$ can be etched very efficiently and with high region specificity by heating in air.
A chemical etching method was developed for (110) and (001) NdGaO3 single crystal substrates in order to obtain an atomically flat GaO2-x - terminated surface. Depending on the surface step density the substrates were etched in pH-controlled NH4F- or NH4Cl-based solutions, followed by an annealing step at temperatures of 800-1000oC, in air or in oxygen flow, in order to recrystallize the surface. Atomic Force Microscopy (AFM) and high-pressure Reflection High Energy Electron Diffraction (RHEED) were used to analyse the surface morphology of the samples after every treatment. Studies on the che…
Near-ambient pressure XPS and STM experiments are performed to study the intercalation of oxygen and nitrogen at different partial gas pressures and different temperatures in the graphene/Ni/Ir(111) system of different morphologies. We performed detailed experiments on the investigation of the chemical state and topography of graphene, before and after gas intercalation, depending on the amount of pre-intercalated Ni in graphene/Ir(111). It is found that only oxygen can be intercalated under graphene in all considered cases, indicating the role of the intra-molecular bonding strength and possi…
In situ plasma etching is a common method to prepare diamond substrates for epitaxial overgrowth to effectuate higher quality. However, there is no practical, direct, qualitative method established so far to assess the performance of the etching pretreatment. We propose an optimization of the pretreatment process on grounds of high-resolution X-ray diffraction measurements to judge the structural quality gain of the diamond substrates and the effectiveness of the polishing-induced subsurface damage removal. The obtained data shows, that parameters like thickness nor misorientation angle of the…
We use low-energy electron microscopy to investigate how graphene is removed from Ru(0001) and Ir(111) by reaction with oxygen. We find two mechanisms on Ru(0001). At short times, oxygen reacts with carbon monomers on the surrounding Ru surface, decreasing their concentration below the equilibrium value. This undersaturation causes a flux of carbon from graphene to the monomer gas. In this initial mechanism, graphene is etched at a rate that is given precisely by the same non-linear dependence on carbon monomer concentration that governs growth. Thus, during both growth and etching, carbon att…
Mn doped GaAs thin films were grown using molecular beam epitaxy at high and low substrate temperatures. The elemental concentration depth profiles in the thin films were determined by using Auger electron spectroscopy combined with ion etching. The Mn concentration is higher near the surface and then decreases with depth for films grown at high substrate temperatures. The Mn concentration profile is much more uniform when films are grown using a low substrate temperature. What was unexpectedly found are high levels of oxygen in the low substrate temperature grown thin films.
Strains strongly affect the properties of low-dimensional materials, such as graphene. By combining in situ, in operando, reflection high energy electron diffraction experiments with first-principles calculations, we show that large strains, above 2%, are present in graphene during its growth by chemical vapor deposition on Ir(111) and when it is subjected to oxygen etching and ion bombardment. Our results unravel the microscopic relationship between point defects and strains in epitaxial graphene and suggest new avenues for graphene nanostructuring and engineering its properties through intro…
Atomic resolution high angle annular dark field imaging of suspended, single-layer graphene, onto which the metals Cr, Ti, Pd, Ni, Al and Au atoms had been deposited was carried out in an aberration corrected scanning transmission electron microscope. In combination with electron energy loss spectroscopy, employed to identify individual impurity atoms, it was shown that nano-scale holes were etched into graphene, initiated at sites where single atoms of all the metal species except for gold come into close contact with the graphene. The e-beam scanning process is instrumental in promoting meta…
Electronic functionalities in materials from silicon to transition metal oxides are to a large extent controlled by defects and their relative arrangement. Outstanding examples are the oxides of copper, where defect order is correlated with their high superconducting transition temperatures. The oxygen defect order can be highly inhomogeneous, even in "optimal" superconducting samples, which raises the question of the nature of the sample regions where the order does not exist but which nonetheless form the "glue" binding the ordered regions together. Here we use scanning X-ray microdiffractio…
The intercalation of an oxide barrier between graphene and its metallic substrate for chem- ical vapor deposition is a contamination-free alternative to the transfer of graphene to dielectric supports, usually needed for the realization of electronic devices. Low-cost pro- cesses, especially at atmospheric pressure, are desirable but whether they are achievable remains an open question. Combining complementary microscopic analysis, providing structural, electronic, vibrational, and chemical information, we demonstrate the spontaneous reactive intercalation of 1.5 nm-thick oxide ribbons between…
