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.

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).

Metamagnetic transition and a loss of magnetic hysteresis caused by electron trapping in monolayers of single-molecule magnet Tb2@C79N.

Realization of stable spin states in surface-supported magnetic molecules is crucial for their applications in molecular spintronics, memory storage or quantum information processing. In this work, we studied the surface magnetism of dimetallo-azafullerene Tb2@C79N, showing a broad magnetic hysteresis in a bulk form. Surprisingly, monolayers of Tb2@C79N exhibited a completely different behavior, with the prevalence of a ground state with antiferromagnetic coupling at low magnetic field and a metamagnetic transition in the magnetic field of 2.5-4 T. Monolayers of Tb2@C79N were deposited onto Cu(111) and Au(111) by evaporation in ultra-high vacuum conditions, and their topography and electronic structure were characterized by scanning tunneling microscopy and spectroscopy (STM/STS). X-ray photoelectron spectroscopy (XPS), in combination with DFT studies, revealed that the nitrogen atom of the azafullerene cage tends to avoid metallic surfaces. Magnetic properties of the (sub)monolayers were then studied by X-ray magnetic circular dichroism (XMCD) at the Tb-M4,5 absorption edge. While in bulk powder samples Tb2@C79N behaves as a single-molecule magnet with ferromagnetically coupled magnetic moments and blocking of magnetization at 28 K, its monolayers exhibited a different ground state with antiferromagnetic coupling of Tb magnetic moments. To understand if this unexpected behavior is caused by a strong hybridization of fullerenes with metallic substrates, XMCD measurements were also performed for Tb2@C79N adsorbed on h-BN|Rh(111) and MgO|Ag(100). The co-existence of two forms of Tb2@C79N was found on these substrates as well, but magnetization curves showed narrow magnetic hysteresis detectable up to 25 K. The non-magnetic state of Tb2@C79N in monolayers is assigned to anionic Tb2@C79N- species with doubly-occupied Tb-Tb bonding orbital and antiferromagnetic coupling of the Tb moments. A charge transfer from the substrate or trapping of secondary electrons are discussed as a plausible origin of these species.

Synthesis of a magnetic π-extended carbon nanosolenoid with Riemann surfaces.

Riemann surfaces are deformed versions of the complex plane in mathematics. Locally they look like patches of the complex plane, but globally, the topology may deviate from a plane. Nanostructured graphitic carbon materials resembling a Riemann surface with helicoid topology are predicted to have interesting electronic and photonic properties. However, fabrication of such processable and large π-extended nanographene systems has remained a major challenge. Here, we report a bottom-up synthesis of a metal-free carbon nanosolenoid (CNS) material with a low optical bandgap of 1.97 eV. The synthesis procedure is rapid and possible on the gram scale. The helical molecular structure of CNS can be observed by direct low-dose high-resolution imaging, using integrated differential phase contrast scanning transmission electron microscopy. Magnetic susceptibility measurements show paramagnetism with a high spin density for CNS. Such a π-conjugated CNS allows for the detailed study of its physical properties and may form the base of the development of electronic and spintronic devices containing CNS species.

High-Quality Hexagonal Boron Nitride from 2D Distillation.

The production of high-quality two-dimensional (2D) materials is essential for the ultimate performance of single layers and their hybrids. Hexagonal boron nitride (h-BN) is foreseen to become the key 2D hybrid and packaging material since it is insulating, impermeable, flat, transparent, and chemically inert, though it is difficult to attain in ultimate quality. Here, a scheme is reported for producing single layer h-BN that shows higher quality in view of mosaicity and strain variations than material from chemical vapor deposition (CVD). We delaminate CVD h-BN from Rh(111) and transfer it to a clean metal surface. The twisting angle between BN and the second substrate yields metastable moiré structures. Annealing above 1000 K leads to 2D distillation, i.e., catalyst-assisted BN sublimation from the edges of the transferred layer and subsequent condensation into superior quality h-BN. This provides a way for 2D material production remote from CVD instrumentation.

Magnetic hysteresis and strong ferromagnetic coupling of sulfur-bridged Dy ions in clusterfullerene Dy2S@C82.

Two isomers of metallofullerene Dy2S@C82 with sulfur-bridged Dy ions exhibit broad magnetic hysteresis with sharp steps at sub-Kelvin temperature. Analysis of the level crossing events for different orientations of a magnetic field showed that even in powder samples, the hysteresis steps caused by quantum tunneling of magnetization can provide precise information on the strength of intramolecular Dy⋯Dy inter-actions. A comparison of different methods to determine the energy difference between ferromagnetic and antiferromagnetic states showed that sub-Kelvin hysteresis gives the most robust and reliable values. The ground state in Dy2S@C82 has ferromagnetic coupling of Dy magnetic moments, whereas the state with antiferromagnetic coupling in C s and C 3v cage isomers is 10.7 and 5.1 cm-1 higher, respectively. The value for the C s isomer is among the highest found in metallofullerenes and is considerably larger than that reported in non-fullerene dinuclear molecular magnets. Magnetization relaxation times measured in zero magnetic field at sub-Kelvin temperatures tend to level off near 900 and 3200 s in C s and C 3v isomers. These times correspond to the quantum tunneling relaxation mechanism, in which the whole magnetic moment of the Dy2S@C82 molecule flips at once as a single entity.

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.

Air-stable redox-active nanomagnets with lanthanide spins radical-bridged by a metal-metal bond.

Engineering intramolecular exchange interactions between magnetic metal atoms is a ubiquitous strategy for designing molecular magnets. For lanthanides, the localized nature of 4f electrons usually results in weak exchange coupling. Mediating magnetic interactions between lanthanide ions via radical bridges is a fruitful strategy towards stronger coupling. In this work we explore the limiting case when the role of a radical bridge is played by a single unpaired electron. We synthesize an array of air-stable Ln2@C80(CH2Ph) dimetallofullerenes (Ln2 = Y2, Gd2, Tb2, Dy2, Ho2, Er2, TbY, TbGd) featuring a covalent lanthanide-lanthanide bond. The lanthanide spins are glued together by very strong exchange interactions between 4f moments and a single electron residing on the metal-metal bonding orbital. Tb2@C80(CH2Ph) shows a gigantic coercivity of 8.2 Tesla at 5 K and a high 100-s blocking temperature of magnetization of 25.2 K. The Ln-Ln bonding orbital in Ln2@C80(CH2Ph) is redox active, enabling electrochemical tuning of the magnetism.

Electronic Properties of Transferable Atomically Thin MoSe2/h-BN Heterostructures Grown on Rh(111).

Vertically stacked two-dimensional (2D) heterostructures composed of 2D semiconductors have attracted great attention. Most of these include hexagonal boron nitride (h-BN) as either a substrate, an encapsulant, or a tunnel barrier. However, reliable synthesis of large-area and epitaxial 2D heterostructures incorporating BN remains challenging. Here, we demonstrate the epitaxial growth of nominal monolayer (ML) MoSe2 on h-BN/Rh(111) by molecular beam epitaxy, where the MoSe2/h-BN layer system can be transferred from the growth substrate onto SiO2. The valence band structure of ML MoSe2/h-BN/Rh(111) revealed by photoemission electron momentum microscopy ( kPEEM) shows that the valence band maximum located at the K point is 1.33 eV below the Fermi level ( EF), whereas the energy difference between K and Γ points is determined to be 0.23 eV, demonstrating that the electronic properties, such as the direct band gap and the effective mass of ML MoSe2, are well preserved in MoSe2/h-BN heterostructures.

Strong carbon cage influence on the single molecule magnetism in Dy-Sc nitride clusterfullerenes.

Magnetic properties of endohedral metallofullerenes with nitride clusters DySc2N and Dy2ScN and different carbon cages are studied by SQUID magnetometry. All molecules behave as single molecule magnets (SMMs) and exhibit magnetic hysteresis. It is found that the blocking temperature of magnetization and relaxation times strongly depend on the fullerene cage, with the C80-Ih isomer offering the best SMM properties.

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.

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.

Selective arc-discharge synthesis of Dy2S-clusterfullerenes and their isomer-dependent single molecule magnetism.

A method for the selective synthesis of sulfide clusterfullerenes Dy2S@C2n is developed. Addition of methane to the reactive atmosphere reduces the formation of empty fullerenes in the arc-discharge synthesis, whereas the use of Dy2S3 as a source of metal and sulfur affords sulfide clusterfullerenes as the main fullerene products along with smaller amounts of carbide clusterfullerenes. Two isomers of Dy2S@C82 with Cs(6) and C3v(8) cage symmetry, Dy2S@C72-Cs(10528), and a carbide clusterfullerene Dy2C2@C82-Cs(6) were isolated. The molecular structure of both Dy2S@C82 isomers was elucidated by single-crystal X-ray diffraction. SQUID magnetometry demonstrates that all of these clusterfullerenes exhibit hysteresis of magnetization, with Dy2S@C82-C3v(8) being the strongest single molecule magnet in the series. DC- and AC-susceptibility measurements were used to determine magnetization relaxation times in the temperature range from 1.6 K to 70 K. Unprecedented magnetization relaxation dynamics with three consequent Orbach processes and energy barriers of 10.5, 48, and 1232 K are determined for Dy2S@C82-C3v(8). Dy2S@C82-Cs(6) exhibits faster relaxation of magnetization with two barriers of 15.2 and 523 K. Ab initio calculations were used to interpret experimental data and compare the Dy-sulfide clusterfullerenes to other Dy-clusterfullerenes. The smallest and largest barriers are ascribed to the exchange/dipolar barrier and relaxation via crystal-field states, respectively, whereas an intermediate energy barrier of 48 K in Dy2S@C82-C3v(8) is assigned to the local phonon mode, corresponding to the librational motion of the Dy2S cluster inside the carbon cage.

Single molecule magnet with an unpaired electron trapped between two lanthanide ions inside a fullerene.

Increasing the temperature at which molecules behave as single-molecule magnets is a serious challenge in molecular magnetism. One of the ways to address this problem is to create the molecules with strongly coupled lanthanide ions. In this work, endohedral metallofullerenes Y2@C80 and Dy2@C80 are obtained in the form of air-stable benzyl monoadducts. Both feature an unpaired electron trapped between metal ions, thus forming a single-electron metal-metal bond. Giant exchange interactions between lanthanide ions and the unpaired electron result in single-molecule magnetism of Dy2@C80(CH2Ph) with a record-high 100 s blocking temperature of 18 K. All magnetic moments in Dy2@C80(CH2Ph) are parallel and couple ferromagnetically to form a single spin unit of 21 µB with a dysprosium-electron exchange constant of 32 cm-1. The barrier of the magnetization reversal of 613 K is assigned to the state in which the spin of one Dy centre is flipped.

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.

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).