High-resolution Electron Energy Loss Spectroscopy Research Articles

Tailoring Heterostructure Growth on Liquid Metal Nanodroplets through Interface Engineering.

Liquid metal (LM) nanodroplets possess intriguing surface properties, thus offering promising potential in chemical synthesis, catalysis, and biomedicine. However, the reaction kinetics and product growth at the surface of LM nanodroplets are significantly influenced by the interface involved, which has not been thoroughly explored and understood. Here, we propose an interface engineering strategy, taking a spontaneous galvanic reaction between Ga0 and AuCl4- ions as a representative example, to successfully modulate the growth of heterostructures on the surface of Ga-based LM nanodroplets by establishing a dielectric interface with a controllable thickness between LM and reactive surroundings. Combining high-resolution electron energy-loss spectroscopy (EELS) analysis and theoretical simulation, it was found that the induced charge distribution at the interface dominates the spatiotemporal distribution of the reaction sites. Employing tungsten oxide (WOx) with varying thicknesses as the demonstrated dielectric interface of LM, Ga@WOx@Au with distinct core-shell-satellite or dimer-like heterostructures has been achieved and exhibited different photoresponsive capabilities for photodetection. Understanding the kinetics of product growth and the regulatory strategy of the dielectric interface provides an experimental approach to controlling the structure and properties of products in LM nanodroplet-involved chemical processes.

N‐Heterocyclic Olefins on a Metallic Surface – Adsorption, Orientation, and Electronic Influence

AbstractN‐Heterocyclic olefins (NHOs), possessing highly polarizable and remarkably electron‐rich double bonds, have been effectively utilized as exceptional anchors for surface modifications. Herein, the adsorption, orientation, and electronic properties of NHOs on a metal surface are investigated. On Cu(111), the sterically low‐demanding IMe‐NHO is compared to its analogous IMe‐NHC counterpart. High‐resolution electron energy‐loss spectroscopy (HREELS) measurements show for both molecules a flat‐lying ring adsorption configuration. While the NHC adopts a dimer configuration including a Cu adatom, the NHO chemisorbs over a C–Cu bond perpendicular to the surface. This distinct difference leads for the IMe‐NHOs to have a higher thermal stability on the surface. Moreover, IMe‐NHOs introduce a higher net electron transfer to the surface compared to the IMe‐NHCs, which results in a stronger effect on the work function. These results highlight the role of NHOs in surface science as they extend the functionalization capabilities of NHCs into stronger electronic modification.

Unveiling Enhanced PEC Water Oxidation: Morphology Tuning and Interfacial Phase Change in α-Fe2O3@K-OMS-2 Branched Core-Shell Nanoarrays.

A simple fabrication method that involves two steps of hydrothermal reaction has been demonstrated for the growth of α-Fe2O3@K-OMS-2 branched core-shell nanoarrays. Different reactant concentrations in the shell-forming step led to different morphologies in the resultant composites, denoted as 0.25 OC, 0.5 OC, and 1.0 OC. Both 0.25 OC and 0.5 OC formed perfect branched core-shell structures, with 0.5 OC possessing longer branches, which were observed by SEM and TEM. The core K-OMS-2 and shell α-Fe2O3 were confirmed by grazing incidence X-ray diffraction (GIXRD), EDS mapping, and atomic alignment from high-resolution STEM images. Further investigation with high-resolution HAADF-STEM, EELS, and XPS indicated the existence of an ultrathin layer of Mn3O4 sandwiched at the interface. All composite materials offered greatly enhanced photocurrent density at 1.23 VRHE, compared to the pristine Fe2O3 photoanode (0.33 mA/cm2), and sample 0.5 OC showed the highest photocurrent density of 2.81 mA/cm2. Photoelectrochemical (PEC) performance was evaluated for the samples by conducting linear sweep voltammetry (LSV), applied bias photo-to-current efficiency (ABPE), electrochemical impedance spectroscopy (EIS), incident-photo-to-current efficiency (IPCE), transient photocurrent responses, and stability tests. The charge separation and transfer efficiencies, together with the electrochemically active surface area, were also investigated. The significant enhancement in sample 0.5 OC is ascribed to the synergetic effect brought by the longer branches in the core-shell structure, the conductive K-OMS-2 core, and the formation of the Mn3O4 thin layer formed between the core and shell.

4H-SiC/SiO2 Interface Degradation in 1.2 kV 4H-SiC MOSFETs due to Power Cycling Tests

Power cycling tests (PCTs) assess the reliability of power devices by closely simulating their operating conditions. A PCT was performed on commercially available 1.2 kV 4H-SiC power metal–oxide–semiconductor field-effect transistors to observe its impact on the 4H-SiC/SiO2 interface. High-resolution transmission electron microscopy and electron energy loss spectroscopy measurements showed variations in the length of the 4H-SiC/SiO2 transition layer, depending on whether the device was power cycled. Moreover, the total resistance at Vg >> Vt in Rtot − (Vg-Vt)−1 graph increased to 16.5%, while it changed more radically to 47.3% at Vg ≈ Vt. The threshold voltage shifted negatively. These variations cannot be expected solely through the wearout of the package.

Oxygen Transport through Amorphous Cathode Coatings in Solid-State Batteries.

All solid-state batteries (SSBs) are considered the most promising path to enabling higher energy-density portable energy, while concurrently improving safety as compared to current liquid electrolyte solutions. However, the desire for high energy necessitates the choice of high-voltage cathodes, such as nickel-rich layered oxides, where degradation phenomena related to oxygen loss and structural densification at the cathode surface are known to significantly compromise the cycle and thermal stability. In this work, we show, for the first time, that even in an SSB, and when protected by an intact amorphous coating, the LiNi0.5Mn0.3Co0.2O2 (NMC532) surface transforms from a layered structure into a rocksalt-like structure after electrochemical cycling. The transformation of the surface structure of the Li3B11O18 (LBO)-coated NMC532 cathode in a thiophosphate-based solid-state cell is characterized by high-resolution complementary electron microscopy techniques and electron energy loss spectroscopy. Ab initio molecular dynamics corroborate facile transport of O2- in the LBO coating and in other typical coating materials. This work identifies that oxygen loss remains a formidable challenge and barrier to long-cycle life high-energy storage, even in SSBs with durable, amorphous cathode coatings, and directs attention to considering oxygen permeability as an important new design criteria for coating materials.

Metal Core-Shell Nanoparticle Supercrystals: From Photoactivation of Hydrogen Evolution to Photocorrosion.

Gas nanobubbles are directly linked to many important chemical reactions. While they can be detrimental to operational devices, they also reflect the local activity at the nanoscale. Here, supercrystals made of highly monodisperse Ag@Pt core-shell nanoparticles are first grown onto a solid support and fully characterized by electron microscopies and X-ray scattering. Supercrystals are then used as a plasmonic photocatalytic platform for triggering the hydrogen evolution reaction. The catalytic activity is measured operando at the single supercrystal level by high-resolution optical microscopy, which allows gas nanobubble nucleation to be probed at the early stage with high temporal resolution and the amount of gas molecules trapped inside them to be quantified. Finally, a correlative microscopy approach and high-resolution electron energy loss spectroscopy help to decipher the mechanisms at the origin of the local degradation of the supercrystals during catalysis, namely nanoscale erosion and corrosion.

Chemical and topological disordering in M23C6 due to irradiation: An atomic-scale observation

To clarify the stability of M23C6 precipitate in steels under irradiation, the chemical and topological disordering behaviors in M23C6 subjected to ion irradiation at elevated temperatures were investigated with the combined application of high-resolution electron microscopy (HREM) and electron energy-loss spectroscopy (EELS). Results show that the duplex structured M23C6 which is the core-crystalline and shell-amorphous was observed in the specimen irradiated at 623 K, nevertheless, no amorphous phase was observed in the specimen irradiated at 673 K. HREM observation confirmed the occurrence of the chemical disordering in irradiated M23C6, and the disordering of W atoms in the M23C6 unit cell was clarified by the peak intensity profile of the atomic column from the HREM image. EELS analyses indicate that no obvious chemical shift was observed by the core-loss spectrum, however, the change in the electron mean free path (λ) due to irradiation was confirmed by the low-loss spectrum, which is related to the formation of both irradiation defects and amorphous phase. It is proposed that the decreased material density upon irradiation is ascribed to the formation of W-vacancy-dominated defect clusters. An obvious change in interatomic distance was not observed in the irradiated M23C6 based on the radical distribution function analysis by extended energy-loss fine structure spectrum. However, the peak intensity decreased by irradiation, confirming the occurrence of chemical and topological disordering, regardless of the carbide being crystalline or amorphous.

Direct Observation of Topological Phonons in Graphene.

Phonons, as the most fundamental emergent bosons in condensed matter systems, play an essential role in the thermal, mechanical, and electronic properties of crystalline materials. Recently, the concept of topology has been introduced to phonon systems, and the nontrivial topological states also exist in phonons due to the constraint by the crystal symmetry of the space group. Although the classification of various topological phonons has been enriched theoretically, experimental studies were limited to several three-dimensional (3D) single crystals with inelastic x-ray or neutron scatterings. The experimental evidence of topological phonons in two-dimensional (2D) materials is absent. Here, using high-resolution electron energy loss spectroscopy following our theoretical predictions, we directly map out the phonon spectra of the atomically thin graphene in the entire 2D Brillouin zone, and observe two nodal-ring phonons and four Dirac phonons. The closed loops of nodal-ring phonons and the conical structure of Dirac phonons in 2D momentum space are clearly revealed by our measurements, in nice agreement with our theoretical calculations. The ability of 3D mapping (2D momentum space and energy space) of phonon spectra opens up a new avenue to the systematic identification of the topological phononic states. Our work lays a solid foundation for potential applications of topological phonons in superconductivity, dynamic instability, and phonon diode.

Using electron energy-loss spectroscopy to measure nanoscale electronic and vibrational dynamics in a TEM.

Electron energy-loss spectroscopy (EELS) can measure similar information to x-ray, UV-Vis, and IR spectroscopies but with atomic resolution and increased scattering cross-sections. Recent advances in electron monochromators have expanded EELS capabilities from chemical identification to the realms of synchrotron-level core-loss measurements and to low-loss, 10-100meV excitations, such as phonons, excitons, and valence structures. EELS measurements are easily correlated with electron diffraction and atomic-scale real-space imaging in a transmission electron microscope (TEM) to provide detailed local pictures of quasiparticle and bonding states. This perspective provides an overview of existing high-resolution EELS (HR-EELS) capabilities while also motivating the powerful next step in the field-ultrafast EELS in a TEM. Ultrafast EELS aims to combine atomic-level, element-specific, and correlated temporal measurements to better understand spatially specific excited-state phenomena. Ultrafast EELS measurements also add to the abilities of steady-state HR-EELS by being able to image the electromagnetic field and use electrons to excite photon-forbidden and momentum-specific transitions. We discuss the technical challenges ultrafast HR-EELS currently faces, as well as how integration with in situ and cryo measurements could expand the technique to new systems of interest, especially molecular and biological samples.

Characterization of Cu-Cu direct bonding in ambient atmosphere enabled using (111)-oriented nanotwinned-copper

The copper-copper (Cu-Cu) direct bonding technology was proposed in recent years in order to realize precise preparation and reliable service under high current density for three-dimension (3D) packaging in the post-Moore-era. In this study, Cu-Cu direct bonding was achieved in the ambient atmosphere by utilizing highly (111) oriented copper with nanotwin structure (called (111) nt-Cu). The thermal compression with a pressure of 30 MPa was conducted on a couple of Cu films at 300 and 400 °C in air. The Cu-Cu joints after bonding were further investigated by scanning electron microscopy (SEM), electron back-scattered diffraction (EBSD) and transmission electron microscopy (TEM). Different from the polycrystalline copper, perfect bonding was achieved as confirmed by high-resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS). The shear strength after air bonding was measured as 96.04 ± 5.67 MPa on average, which demonstrated relatively high performance in traditional Cu-Cu bonding. The excellent resistance to oxidation and fast Cu(111) surface diffusivity of (111) nt-Cu guaranteed the bonding process. Above all, the achievement of (111) nt-Cu high performance bonding in the ambient atmosphere should give an insight into developing new interconnected technology.

Mechanistic Understanding of Ring-Opening of Tetrahydrofurfuryl Alcohol over WOx-Modified Pt Model Surfaces and Powder Catalysts

The upgrading of heterocyclic biomass-derived oxygenates such as tetrahydrofurfuryl alcohol (THFA) via ring-opening is a promising pathway to produce value-added diol molecules using renewable carbon sources. This study combines model surface experiments, first-principles calculations, and powder catalyst characterization and activity evaluation to unravel the nature of the Pt and WOx active sites and the reaction mechanism of the THFA ring-opening reaction on a WOx/Pt inverse oxide catalyst. Temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) measurements on model surfaces demonstrated that THFA ring opened on Pt(111) but underwent further decomposition due to its strong bonding with the surface. However, WOx deposited on Pt(111) altered the interaction strength between the ring-opened intermediate and the surface to a proper extent to facilitate the facile desorption of the desired 1,5-pentanediol (1,5-PeD) product. Density functional theory (DFT) calculations showed that WOx/Pt(111) could promote ring opening of THFA via an oxocarbenium ion-like transition state, which was stabilized by hydrogen bonding with the hydroxyl groups of WOx. The hydrogenation of the ring-opened 5-hydroxyvaleraldehyde intermediate to 1,5-PeD was then feasible via Brønsted acid sites present on WOx. Steady-state activity studies on the corresponding powder catalysts showed that the 1,5-PeD selectivity increased from 20% on Pt/SiO2 to 65% on WOx/Pt/SiO2 with 1 wt % WOx loading, consistent with model surface experiments and DFT calculations. This study demonstrates the feasibility of using model surface experiments and first-principles calculations to guide practical catalyst design, and provides a design strategy that can be applied to the selective ring-opening of relevant heterocyclic biomass-derived oxygenates.

How positioning of a hard ceramic TiB2 layer in Al/CuO multilayers can regulate the overall energy release behavior

This study reports on a new ternary thermite comprising of Al-TiB2/CuO multilayers, designed to take the advantage of high ignitability of titanium (Ti), high volumetric density of boron (B), and low melting point of aluminum (Al). Results demonstrate synergetic effects leading to an energetic layer outperforming its single fuel counterparts, Al/CuO or TiB2/CuO, while being safe to handle. The additive TiB2 not only lowers the ignition energy by 100%, but also enhances the burn rate by more than a factor of two compared to the single fuel samples (Al/CuO and TiB2/CuO). The thermite reaction sequences and synergy of Ti, B and Al oxidation, examined by thermo-analytical analyses coupled with X-ray spectroscopy and high-resolution electron energy loss spectroscopy, demonstrate the strong affinity of TiB2 to oxygen that catalyzes CuO decomposition at temperatures as low as 380 °C; followed by a dual-step TiB2 oxidation: first to TiO, and then to TiO2 led by a reaction limiting step of oxidizer availability. Finally, Al undergoes oxidation via liquid boron oxide as well as gaseous oxygen. This study also underlines the crucial effect of the nanolayer morphology in the thin-film technology: when Al is sputter-deposited onto the TiB2 layer, Al ions penetrate into the grain boundaries penalizing TiB2 reactivity. The results demonstrate the advantages of using TiB2 fuel to improve the ignitability and the combustion performance of Al based thermite and offer some means to finely tune the energetic properties.

Nodal-line plasmons in ZrSiX ( X=S,Se,Te ) and their temperature dependence

Topological nodal-line semimetals gain extensive attention for their peculiar linear band crossings along closed lines in the Brillouin zone leading to various interesting properties. Here, we systematically study the nodal-line plasmons of prototypical nodal-line semimetals $\mathrm{ZrSi}X$ ($X=\mathrm{S},\mathrm{Se},\mathrm{Te}$) by high-resolution electron energy loss spectroscopy, and first-principles calculations. In energy range from near- to mid-infrared frequencies, plasmons induced by the intraband correlations ($\ensuremath{\sim}0.8$ eV) and the interband correlations ($\ensuremath{\sim}0.3$ eV) of surface states related to the nodal-line electrons are universally observed in all the $\mathrm{ZrSi}X$ family. The bulk plasmon ($\ensuremath{\sim}0.6$ eV) is observed in ZrSiS but is indiscernible in both ZrSiSe and ZrSiTe owing to their stronger screening effect from the surface states and large interlayer distance. Although the plasmons in ZrSiS seem to be temperature independent, the frequencies of the intraband plasmons in ZrSiSe and ZrSiTe show large redshifts ($\ensuremath{\sim}10%$) with temperature increasing from 30 K to room temperature, which can be ascribed to the prominent thermal occupation effect of nodal-line electrons when the Fermi level is close to the nodal line.

Formation of Graphene on Gold–Nickel Surface Alloys

Nickel (Ni)-catalyzed growth of a single- or rotated-graphene layer is a well-established process above 800 K. In this report, a Au-catalyzed, low-temperature, and facile route at 500 K for graphene formation is described. The substantially lower temperature is enabled by the presence of a surface alloy of Au atoms embedded within Ni(111), which catalyzes the outward segregation of carbon atoms buried in the Ni bulk at temperatures as low as 400-450 K. The resulting surface-bound carbon in turn coalesces into graphene above 450-500 K. Control experiments on a Ni(111) surface show no evidence of carbon segregation or graphene formation at these temperatures. Graphene is identified by its out-of-plane optical phonon mode at 750 cm-1 and its longitudinal/transverse optical phonon modes at 1470 cm-1 while surface carbon is identified by its C-Ni stretch mode at 540 cm-1, as probed by high-resolution electron energy-loss spectroscopy. Dispersion measurements of the phonon modes confirm the presence of graphene. Graphene formation is observed to be maximum at 0.4 ML Au coverage. The results of these systematic molecular-level investigations open the door to graphene synthesis at the low temperatures required for integration with complementary metal-oxide-semiconductor processes.

The effect of ammonia addition on soot nanostructure and composition in ethylene laminar flames

The formation of soot in ammonia (NH3) combustion with a hydrocarbon such as ethylene (C2H4) is investigated using the analysis of particles’ nanostructure and surface chemical composition to identify the mechanisms by which NH3 suppresses soot growth. Young and mature soot particles were extracted from laminar diffusion co-flow flames of NH3C2H4 blends up to 50% NH3. The soot nanostructure is examined using lattice fringe analysis of high-resolution transmission electron microscopy (HRTEM) images, Raman Spectroscopy, and Electron Energy Loss Spectroscopy (EELS). The chemical composition of the soot surface is analyzed using X-ray Photoelectron Spectroscopy (XPS). With increasing NH3 addition, reduced planar growth of the soot graphitic layers is observed through the analysis of the soot nanostructure which indicates the suppression of carbon addition at the edge sites of the layer planes. It is also found that the carbon sp2/sp3 bonding ratio increases which shows a nanostructure with less carbon sp3 bonding at defect sites. By exploring the chemical composition, the nitrogen content of the soot surface increases with NH3 addition which is caused by the bonding of nitrogenated species with carbon at defect and edge sites of the carbon layer, reducing the potential for carbon addition, and thus soot growth. The results also show an increased risk of formation of nitrogenated polyaromatic hydrocarbons (N-PAHs) on the soot surface by NH3 addition. The study presents a novel investigation of the impact of NH3 on the soot surface chemistry and particles nanostructure which explains the role of NH3 in suppressing soot growth and reveals the potential for new toxic characteristics for the soot emissions formed in NH3-hydrocarbon cofired systems.

Entropy-Stabilized Multicomponent Porous Spinel Nanowires of NiFeXO4 (X = Fe, Ni, Al, Mo, Co, Cr) for Efficient and Durable Electrocatalytic Oxygen Evolution Reaction in Alkaline Medium.

Cost-effective electrochemical water splitting technology hinges on the development of efficient and durable catalysts for oxygen evolution reaction (OER). Spinel oxides (formula: AxB3-xO4) are structurally stable for real applications. Much effort has been devoted to improving the catalytic activity. Here, we report a eutectic dealloying strategy to activate the porous spinel NiFe2O4 nanowires with up to four metal cation substitutions. As-obtained spinel NiFeXO4 (X = Fe, Ni, Al, Mo, Co, Cr) delivers a benchmark current density of 10 mA·cm-2 at an overpotential of only 195 mV, outperforming most spinel phase OER electrocatalysts and comparable to the state-of-the-art NiFe hydroxides. It is stable for over 115 h of electrolysis. Aberration-corrected transmission electron microscopy, high-resolution electron energy loss spectroscopy, and atomic-scale strain mappings reveal that the multivalent cation substitutions result in substantial lattice distortion and significant electronic coupling of metal 3d and O 2p orbitals for increased covalency. Further theoretical calculations suggest that the NiFeXO4 are stabilized by the high configurational entropy, and their synergy favors the absorption of H2O molecules and lowers the adsorption energy barrier of the OOH* intermediate. The improved intrinsic activity together with the highly nanoporous structures contribute to the appealing apparent catalytic performances. The work demonstrates an effective approach for the synthesis of stable multicomponent spinel oxides and highlights the effectiveness of the multication substitution strategy for producing highly durable and active spinel catalysts, which meet multiplexed structure and superior property requirements in practical applications.

Influence of N-introduction on the electronic structure and properties of polyacenes: experiment and quantum chemistry in concert.

N-Heteropolycycles (NHPCs) represent a promising substance class for applications in functional organic materials, since their electronic structure and the resulting individual molecular properties are efficiently tuneable by number and position of nitrogen atoms in the aromatic structural backbone. The isosteric replacement of a C-H unit by N leaves the geometric structure unchanged, while ionization potential, electron affinity and absorption spectra are altered. In this prespective, we present the potent combination of two-photon photoelectron spectroscopy (2PPE) and high-resolution electron energy loss spectroscopy (HREELS) with quantum chemical calculations for the investigation of the electronic structure of NHCPs. In contrast to conventional optical spectroscopies, 2PPE provides insight into electron-detached and attached electronic states of NHCPs, while HREELS delivers the energetic position of the lowest triplet states. Based on our comprehensive investigations, an extension of Platt's famous nomenclature of the low-lying excited ππ* states could be suggested for NHPCs based on the physical properties of the corresponding excitons. Also, the influence of N-introduction onto the occurrence of the so-called α-band in NHPCs compared to the parent polycyclic aromatic hydrocarbons could be explained in detail. While N-substitution of C-H in polycyclic aromatic hydrocarbons (PAHs) is often seen as a simple isosteric replacement, it has a strong influence on the electronic structure and the resulting properties. Therefore rules derived for PAHs can often only be transferred to a limited extent or not at all.

Impact of Connectivity on the Electronic Structure of N-Heterotriangulenes

N-heterotriangulenes (N-HTAs) are promising organic semiconductors for applications in field effect transistors and solar cells. Thereby the electronic structure of organic/metal interfaces and thin films is essential for the performance of organic-molecule-based devices. Here, we studied the structural and the electronic properties of two different N-HTAs, N-HTA 550 and N-HTA 557, the latter containing an additional 7-membered ring, adsorbed on Au(111) using vibrational and electronic high-resolution electron energy loss spectroscopy in combination with state-of-the-art quantum chemical calculations. In the mono- and multilayer, both N-HTAs adopt a planar adsorption geometry with the molecular backbone oriented parallel to the gold substrate. The energies of the lowest excited electronic singlet states (S) are assigned. The optical gap (S0 → S1 transition) is found to be 3.4 eV for N-HTA 550 and 2.5 eV for N-HTA 557. Thus, the introduction of the −C═C– double bond in N-HTA 557 resulted in a pronounced decrease of the optical gap size by 0.9 eV due to the larger π-conjugated electron system compared to N-HTA 550. Structural variations or substitution patterns in N-HTAs foster the opportunity for tailoring their electronic properties.

Theory of spin-polarized high-resolution electron energy loss spectroscopy from nonmagnetic surfaces with a large spin-orbit coupling

The scattering theory of low-energy (slow) electrons has been developed by Evans and Mills [Phys. Rev. B 5, 4126 (1972)]. The formalism is merely based on the electrostatic Coulomb interaction of the scattering electrons with the charge-density fluctuations above the surface and can describe most of the interesting features observed in the high-resolution electron energy-loss spectroscopy experiments. Here we extend this theory by including the spin-orbit coupling in the scattering process. We discuss the impact of this interaction on the scattering cross section. In particular, we discuss cases in which a spin-polarized electron beam is scattered from nonmagnetic surfaces with a strong spin-orbit coupling. We show that under some assumptions one can derive an expression for the scattering cross section, which can be used for numerical calculations of the spin-polarized spectra recorded by spin-polarized high-resolution electron energy-loss spectroscopy experiments.

Termination of graphene edges created by hydrogen and deuterium plasmas

Edge engineering is important for both fundamental research and applications as the device size decreases to nanometer scale. This is especially the case for graphene because a graphene edge shows totally different electronic properties depending on the atomic structure and the termination. It has recently been shown that an atomically precise zigzag edge can be obtained by etching graphene and graphite using hydrogen (H) plasma. However, edge termination had not been studied directly. In this study, termination of edges created by H-plasma is studied by high-resolution electron energy loss spectroscopy to show that the edge is sp2 bonded and the edge carbon atom is terminated by only one H atom. This suggests that an ideal zigzag edge, which is not only atomically precise but also sp2 bonding, can be obtained by H-plasma etching. Etching of the graphite surface with plasma of a different isotope, deuterium (D), is also studied by scanning tunneling microscopy to show that D-plasma anisotropically etches graphite less efficiently, although it can make defects more efficiently, than H-plasma.