Reading and writing single-atom magnets.

The single-atom bit represents the ultimate limit of the classical approach to high-density magnetic storage media. So far, the smallest individually addressable bistable magnetic bits have consisted of 3-12 atoms. Long magnetic relaxation times have been demonstrated for single lanthanide atoms in molecular magnets, for lanthanides diluted in bulk crystals, and recently for ensembles of holmium (Ho) atoms supported on magnesium oxide (MgO). These experiments suggest a path towards data storage at the atomic limit, but the way in which individual magnetic centres are accessed remains unclear. Here we demonstrate the reading and writing of the magnetism of individual Ho atoms on MgO, and show that they independently retain their magnetic information over many hours. We read the Ho states using tunnel magnetoresistance and write the states with current pulses using a scanning tunnelling microscope. The magnetic origin of the long-lived states is confirmed by single-atom electron spin resonance on a nearby iron sensor atom, which also shows that Ho has a large out-of-plane moment of 10.1 ± 0.1 Bohr magnetons on this surface. To demonstrate independent reading and writing, we built an atomic-scale structure with two Ho bits, to which we write the four possible states and which we read out both magnetoresistively and remotely by electron spin resonance. The high magnetic stability combined with electrical reading and writing shows that single-atom magnetic memory is indeed possible.

The Winner Takes It All: Carbon Supersedes Hexagonal Boron Nitride with Graphene on Transition Metals at High Temperatures.

The production of high-quality hexagonal boron nitride (h-BN) is essential for the ultimate performance of 2D materials-based devices, since it is the key 2D encapsulation material. Here, a decisive guideline is reported for fabricating high-quality h-BN on transition metals. It is crucial to exclude carbon from the h-BN related process, otherwise carbon prevails over boron and nitrogen due to its larger binding energy, thereupon forming graphene on metals after high-temperature annealing. The surface reaction-assisted conversion from h-BN to graphene with high-temperature treatments is demonstrated. The pyrolysis temperature Tp is an important quality indicator for h-BN/metals. When the temperature is lower than Tp , the quality of the h-BN layer is improved upon annealing. While the annealing temperature is above Tp , in case of carbon-free conditions, the h-BN disintegrates and nitrogen desorbs from the surface more easily than boron, eventually leading to clean metal surfaces. However, once the h-BN layer is exposed to carbon, graphene forms on Pt(111) in the high-temperature regime. This not only provides an indispensable principle (avoid carbon) for fabricating high-quality h-BN materials on transition metals, but also offers a straightforward method for the surface reaction-assisted conversion from h-BN to graphene on Pt(111).

Switching stiction and adhesion of a liquid on a solid.

When a gecko moves on a ceiling it makes use of adhesion and stiction. Stiction--static friction--is experienced on microscopic and macroscopic scales and is related to adhesion and sliding friction. Although important for most locomotive processes, the concepts of adhesion, stiction and sliding friction are often only empirically correlated. A more detailed understanding of these concepts will, for example, help to improve the design of increasingly smaller devices such as micro- and nanoelectromechanical switches. Here we show how stiction and adhesion are related for a liquid drop on a hexagonal boron nitride monolayer on rhodium, by measuring dynamic contact angles in two distinct states of the solid-liquid interface: a corrugated state in the absence of hydrogen intercalation and an intercalation-induced flat state. Stiction and adhesion can be reversibly switched by applying different electrochemical potentials to the sample, causing atomic hydrogen to be intercalated or not. We ascribe the change in adhesion to a change in lateral electric field of in-plane two-nanometre dipole rings, because it cannot be explained by the change in surface roughness known from the Wenzel model. Although the change in adhesion can be calculated for the system we study, it is not yet possible to determine the stiction at such a solid-liquid interface using ab initio methods. The inorganic hybrid of hexagonal boron nitride and rhodium is very stable and represents a new class of switchable surfaces with the potential for application in the study of adhesion, friction and lubrication.

Single-Molecule Magnets DyM2 N@C80 and Dy2 MN@C80 (M=Sc, Lu): The Impact of Diamagnetic Metals on Dy3+ Magnetic Anisotropy, Dy⋠⋠⋠Dy Coupling, and Mixing of Molecular and Lattice Vibrations.

The substitution of scandium in fullerene single-molecule magnets (SMMs) DySc2 N@C80 and Dy2 ScN@C80 by lutetium has been studied to explore the influence of the diamagnetic metal on the SMM performance of dysprosium nitride clusterfullerenes. The use of lutetium led to an improved SMM performance of DyLu2 N@C80 , which shows a higher blocking temperature of magnetization (TB =9.5 K), longer relaxation times, and broader hysteresis than DySc2 N@C80 (TB =6.9 K). At the same time, Dy2 LuN@C80 was found to have a similar blocking temperature of magnetization to Dy2 ScN@C80 (TB =8 K), but substantially different interactions between the magnetic moments of the dysprosium ions in the Dy2 MN clusters. Surprisingly, although the intramolecular dipolar interactions in Dy2 LuN@C80 and Dy2 ScN@C80 are of similar strength, the exchange interactions in Dy2 LuN@C80 are close to zero. Analysis of the low-frequency molecular and lattice vibrations showed strong mixing of the lattice modes and endohedral cluster librations in k-space. This mixing simplifies the spin-lattice relaxation by conserving the momentum during the spin flip and helping to distribute the moment and energy further into the lattice.

Catalyst Proximity-Induced Functionalization of h-BN with Quat Derivatives.

Inert single-layer boron nitride (h-BN) grown on a catalytic metal may be functionalized with quaternary ammonium compounds (quats) that are widely used as nonreactive electrolytes. We observe that the quat treatment, which facilitates the electrochemical transfer of two-dimensional materials, involves a decomposition of quat ions and leads to covalently bound quat derivatives on top of the 2D layer. Applying tetraoctylammonium and h-BN on rhodium, the reaction product is top-alkylized h-BN as identified with high-resolution X-ray photoelectron spectroscopy. The alkyl chains are homogeneously distributed across the surface, and the properties thereof are well-tunable by the choice of different quats. The functionalization further weakens the 2D material-substrate interaction and promotes easy transfer. Therefore, the functionalization scheme that is presented enables the design of 2D materials with tailored properties and with the freedom to position and orient them as required. The mechanism of this functionalization route is investigated with density functional theory calculations, and we identify the proximity of the catalytic metal substrate to alter the chemical reactivity of otherwise inert h-BN layers.

Centimeter-Sized Single-Orientation Monolayer Hexagonal Boron Nitride With or Without Nanovoids.

Large-area hexagonal boron nitride (h-BN) promises many new applications of two-dimensional materials, such as the protective packing of reactive surfaces or as membranes in liquids. However, scalable production beyond exfoliation from bulk single crystals remained a major challenge. Single-orientation monolayer h-BN nanomesh is grown on 4 in. wafer single crystalline rhodium films and transferred on arbitrary substrates such as SiO2, germanium, or transmission electron microscopy grids. The transfer process involves application of tetraoctylammonium bromide before electrochemical hydrogen delamination. The material performance is demonstrated with two applications. First, protective sealing of h-BN is shown by preserving germanium from oxidation in air at high temperatures. Second, the membrane functionality of the single h-BN layer is demonstrated in aqueous solutions. Here, we employ a growth substrate intrinsic preparation scheme to create regular 2 nm holes that serve as ion channels in liquids.

Surface science at the PEARL beamline of the Swiss Light Source.

The Photo-Emission and Atomic Resolution Laboratory (PEARL) is a new soft X-ray beamline and surface science laboratory at the Swiss Light Source. PEARL is dedicated to the structural characterization of local bonding geometry at surfaces and interfaces of novel materials, in particular of molecular adsorbates, nanostructured surfaces, and surfaces of complex materials. The main experimental techniques are soft X-ray photoelectron spectroscopy, photoelectron diffraction, and scanning tunneling microscopy (STM). Photoelectron diffraction in angle-scanned mode measures bonding angles of atoms near the emitter atom, and thus allows the orientation of small molecules on a substrate to be determined. In energy scanned mode it measures the distance between the emitter and neighboring atoms; for example, between adsorbate and substrate. STM provides complementary, real-space information, and is particularly useful for comparing the sample quality with reference measurements. In this article, the key features and measured performance data of the beamline and the experimental station are presented. As scientific examples, the adsorbate-substrate distance in hexagonal boron nitride on Ni(111), surface quantum well states in a metal-organic network of dicyano-anthracene on Cu(111), and circular dichroism in the photoelectron diffraction of Cu(111) are discussed.

Switching Molecular Conformation with the Torque on a Single Magnetic Moment.

For the endohedral fullerene molecule HoLu_{2}N@C_{80}, it is shown that the endohedral HoLu_{2}N unit may be oriented in a magnetic field. The Ho magnetic moment is fixed in the strong ligand field and aligns along the holmium-nitrogen axis. The torque of a magnetic field on the Ho magnetic moment leads to a hopping bias of the endohedral unit inclining to an orientation parallel to the externally applied field. This endohedral cluster distribution remains frozen below the onset of thermally induced rotation of the endohedral units. We derive an analytical statistical model for the description of the effect that scales below 7 T with the square of the external field strength, and that allows us to resolve the freezing temperature of the endohedral hopping motion. The freezing temperature is around 55 K and depends on the cooling rate, which in turn determines an activation energy for the hopping motion of 185 meV and a prefactor of 1.8×10^{14} s^{-1}. For TbSc_{2}N@C_{80} we find the same behavior with a 3.5% higher freezing temperature.

Mononuclear Clusterfullerene Single-Molecule Magnet Containing Strained Fused-Pentagons Stabilized by a Nearly Linear Metal Cyanide Cluster.

Fused-pentagons results in an increase of local steric strain according to the isolated pentagon rule (IPR), and for all reported non-IPR clusterfullerenes multiple (two or three) metals are required to stabilize the strained fused-pentagons, making it difficult to access the single-atom properties. Herein, we report the syntheses and isolations of novel non-IPR mononuclear clusterfullerenes MNC@C76 (M=Tb, Y), in which one pair of strained fused-pentagon is stabilized by a mononuclear cluster. The molecular structures of MNC@C76 (M=Tb, Y) were determined unambiguously by single-crystal X-ray diffraction, featuring a non-IPR C2v (19138)-C76 cage entrapping a nearly linear MNC cluster, which is remarkably different from the triangular MNC cluster within the reported analogous clusterfullerenes based on IPR-obeying C82 cages. The TbNC@C76 molecule is found to be a field-induced single-molecule magnet (SMM).

Triangular Monometallic Cyanide Cluster Entrapped in Carbon Cage with Geometry-Dependent Molecular Magnetism.

Clusterfullerenes are capable of entrapping a variety of metal clusters within carbon cage, for which the entrapped metal cluster generally keeps its geometric structure (e.g., bond distance and angle) upon changing the isomeric structure of fullerene cage, and whether the properties of the entrapped metal cluster is geometry-dependent remains unclear. Herein we report an unusual triangular monometallic cluster entrapped in fullerene cage by isolating several novel terbium cyanide clusterfullerenes (TbNC@C82) with different cage isomeric structures. Upon varying the isomeric structure of C82 cage from C2(5) to Cs(6) and to C2v(9), the entrapped triangular TbNC cluster exhibits significant distortions as evidenced by the changes of Tb-C(N) and C-N bond distances and variation of the Tb-C(N)-N(C) angle by up to 20°, revealing that the geometric structure of the entrapped triangular TbNC cluster is variable. All three TbNC@C82 molecules are found to be single-ion magnets, and the change of the geometric structure of TbNC cluster directly leads to the alternation of the magnetic relaxation time of the corresponding TbNC@C82 clusterfullerene.

Surface aligned magnetic moments and hysteresis of an endohedral single-molecule magnet on a metal.

The interaction between the endohedral unit in the single-molecule magnet Dy_{2}ScN@C_{80} and a rhodium (111) substrate leads to alignment of the Dy 4f orbitals. The resulting orientation of the Dy_{2}ScN plane parallel to the surface is inferred from comparison of the angular anisotropy of x-ray absorption spectra and multiplet calculations in the corresponding ligand field. The x-ray magnetic circular dichroism is also angle dependent and signals strong magnetocrystalline anisotropy. This directly relates geometric and magnetic structure. Element specific magnetization curves from different coverages exhibit hysteresis at a sample temperature of ∼4 K. From the measured hysteresis curves, we estimate the zero field remanence lifetime during x-ray exposure of a submonolayer to be about 30 seconds.

Methane as a Selectivity Booster in the Arc-Discharge Synthesis of Endohedral Fullerenes: Selective Synthesis of the Single-Molecule Magnet Dy2TiC@C80 and Its Congener Dy2TiC2@C80.

The use of methane as a reactive gas dramatically increases the selectivity of the arc-discharge synthesis of M-Ti-carbide clusterfullerenes (M=Y, Nd, Gd, Dy, Er, Lu). Optimization of the process parameters allows the synthesis of Dy2TiC@C80-I and its facile isolation in a single chromatographic step. A new type of cluster with an endohedral acetylide unit, M2TiC2@C80, is discovered along with the second isomer of M2TiC@C80. Dy2TiC@C80-(I,II) and Dy2TiC2@C80-I are shown to be single-molecule magnets (SMM), but the presence of the second carbon atom in the cluster Dy2TiC2@C80 leads to substantially poorer SMM properties.

The metallofullerene field-induced single-ion magnet HoSc2 N@C80.

The low-temperature magnetic properties of the endohedral metallofullerene HoSc2 N@C80 have been studied by superconducting quantum interference device (SQUID) magnetometry. Alternating current (ac) susceptibility measurements reveal that this molecule exhibits slow relaxation of magnetization in a small applied field with timescales in the order of milliseconds. The equilibrium magnetic properties of HoSc2 N@C80 indicate strong magnetic anisotropy. The large differences in magnetization relaxation times between the present compound and the previously investigated DySc2 N@C80 are discussed.

Chemical vapor deposition and characterization of aligned and incommensurate graphene/hexagonal boron nitride heterostack on Cu(111).

Two limiting factors for a new technology of graphene-based electronic devices are the difficulty of growing large areas of defect-free material and the integration of graphene with an atomically flat and insulating substrate material. Chemical vapor deposition (CVD) on metal surfaces, in particular on copper, may offer a solution to the first problem, while hexagonal boron nitride (h-BN) has been identified as an ideal insulating substrate material. The bottom-up growth of graphene/h-BN stacks on copper surfaces appears therefore as a promising route for future device fabrication. As an important step, we demonstrate the consecutive growth of well-aligned graphene on h-BN, both as single layers, by low-pressure CVD on Cu(111) in an ultrahigh vacuum environment. The resulting films show a largely predominant orientation, defined by the substrate, where the graphene lattice aligns parallel to the h-BN lattice, while each layer maintains its own lattice constant. The lattice mismatch of 1.6% between h-BN and graphene leads to a moiré pattern with a periodicity of about 9 nm, as observed with scanning tunneling microscopy. Accordingly, angle-resolved photoemission data reveal two slightly different Brillouin zones for electronic states localized in graphene and in h-BN, reflecting the vertical decoupling of the two layers. The graphene appears n-doped and shows no gap opening at the K[overline] point of the two-dimensional Brillouin zone.

Immobilizing individual atoms beneath a corrugated single layer of boron nitride.

Single atoms, and in particular the least reactive noble gases, are difficult to immobilize at room temperature. Ion implantation into a crystal lattice has this capability, but the randomness of the involved processes does not permit much control over their distribution within the solid. Here we demonstrate that the boron nitride nanomesh, a corrugated single layer of hexagonal boron nitride (h-BN) with a 3.2 nm honeycomb superstructure formed on a Rh(111) surface, can trap individual argon atoms at distinct subsurface sites at room temperature. A kinetic energy window for implantation is identified where the argon ions can penetrate the h-BN layer but not enter the Rh lattice. Scanning tunneling microscopy and photoemission data show the presence of argon atoms at two distinct sites within the nanomesh unit cell, confirmed also by density functional theory calculations. The single atom implants are stable in air. Annealing of implanted structures to 900 K induces the formation of highly regular holes of 2 nm diameter in the h-BN layer with adjacent flakes of the same size found on top of the layer. We explain this "can-opener" effect by the presence of a vacancy defect, generated during the penetration of the Ar ion through the h-BN lattice, and propagating along the rim of a nanomesh pore where the h-BN lattice is highly bent. The reported effects are also observed in graphene on ruthenium and for neon atoms.

Growing sp2 materials on transition metals: calculated atomic adsorption energies of hydrogen, boron, carbon, nitrogen, and oxygen atoms, C2 and BN dimers, C6 and (BN)3 hexamers, graphene and h-BN with and without atomic vacancies.

The growth of graphene and hexagonal boron nitride on hot transition metal surfaces involves the adsorption of precursor molecules, and their dissociation and assembly into two-dimensional honeycomb lattices. In a recent account it was found that h-BN may be distilled on a rhodium metal surface, which yields higher quality h-BN [Cun et al., ACS Nano, 2020, 15, 1351]. In this context, we calculated in a systematic approach the adsorption energies and sites of hydrogen, boron, carbon, nitrogen, and oxygen atoms and from the site dependence the activation energy for diffusion. Existing computed values of the solvation energy into the bulk were compared to the present ones with our calculation scheme and found to be in good agreement. For the distinction of different systems we introduce the concepts of epiphilicity and epiphobicity. The adsorption energies and stabilities of the C2 and BN dimers, the C6 and (BN)3 ring-hexamers and the graphene and h-BN monolayers allow the prediction of the performance of different substrates in chemical vapor deposition (CVD) processes for the growth of graphene and h-BN. Finally, vacancy creation energies were calculated as a criterion for the stability of graphene and h-BN on metallic substrates.

An endohedral single-molecule magnet with long relaxation times: DySc2N@C80.

The magnetism of DySc(2)N@C(80) endofullerene was studied with X-ray magnetic circular dichroism (XMCD) and a magnetometer with a superconducting quantum interference device (SQUID) down to temperatures of 2 K and in fields up to 7 T. XMCD shows hysteresis of the 4f spin and orbital moment in Dy(III) ions. SQUID magnetometry indicates hysteresis below 6 K, while thermal and nonthermal relaxation is observed. Dilution of DySc(2)N@C(80) samples with C(60) increases the zero-field 4f electron relaxation time at 2 K to several hours.

Chiral distortion of confined ice oligomers (N = 5,6).

Ice nuclei have been studied on the hexagonal boron nitride nanomesh (h-BN/Rh(111)), a template with 2 nm wide molecule traps. Scanning tunneling microscopy shows confined clusters, where oligomers with three protrusions are particularly abundant. Together with local barrier height dI/dz maps, it is found that the dipoles of the water molecules arrange in a homodrome, which is consistent with density functional theory calculations. Hydrogen bonds toward the substrate identify h-BN/Rh(111) to be hydrophilic. The substrate distorts the hexamers (n = 6) and possibly pentamers (n = 5), where the experimentally observed footprints of the three protrusions appear more chiral than expected.