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Van der Waals (vdW) stacking is a powerful technique to achieve desired properties in condensed matter systems through layer-by-layer crystal engineering. A remarkable example is the control over the twist angle between artificially-stacked vdW crystals, enabling the realization of unconventional phenomena in moiré structures ranging from superconductivity to strongly correlated magnetism. Here, we report the appearance of unusual 120° twisted faults in vdW magnet CrI3 crystals. In exfoliated samples, we observe vertical twisted domains with a thickness below 10 nm. The size and distribution of twisted domains strongly depend on the sample preparation methods, with as-synthesized unexfoliated samples showing tenfold thicker domains than exfoliated samples. Cooling induces changes in the relative populations among different twisting domains, rather than the previously assumed structural phase transition to the rhombohedral stacking. The stacking disorder induced by sample fabrication processes may explain the unresolved thickness-dependent magnetic coupling observed in CrI3. Artificial stacking of van der Waals materials is an effective method to design and investigate emergent physical properties in condensed matter systems. Here, the authors characterize the natural twisted layer structure of CrI3, showing its dependence on the sample fabrication process and its implications for the magnetic properties of the material. [ABSTRACT FROM AUTHOR]

CrI3 has raised as an important system to the emergent field of two-dimensional van der Waals magnetic materials. However, it is still unclear why CrI3 which has a ferromagnetic rhombohedral structure in bulk, changed to anti-ferromagnetic monoclinic at thin layers. Here we show that this behaviour is due to the coexistence of both monoclinic and rhombohedral crystal phases followed by three magnetic transitions at TC1 = 61 K, TC2 = 50 K and TC3 = 25 K. Each transition corresponds to a certain fraction of the magnetically ordered volume as well as monoclinic and rhombohedral proportion. The different phases are continuously accessed as a function of the temperature over a broad range of magnitudes. Our findings suggest that the challenge of understanding the magnetic properties of thin layers CrI3 is in general a coexisting structural-phase problem mediated by the volume-wise competition between magnetic phases already present in bulk. CrI3 is a popular van der Waals magnet that exhibits anomalous magnetic properties between bulk and thin layers due to different crystal symmetry. Here, the authors report the coexistence of different magnetostructural phases over the entire range of temperatures, solving a long-standing puzzle. [ABSTRACT FROM AUTHOR]

Designer heterostructures can now be assembled layer-by-layer with unmatched precision thanks to the recently developed deterministic placement methods to transfer two-dimensional (2D) materials. This possibility constitutes the birth of a very active research field on the so-called van der Waals heterostructures. Moreover, these deterministic placement methods also open the door to fabricate complex devices, which would be otherwise very difficult to achieve by conventional bottom-up nanofabrication approaches, and to fabricate fully-encapsulated devices with exquisite electronic properties. The integration of 2D materials with existing technologies such as photonic and superconducting waveguides and fiber optics is another exciting possibility. Here, we review the state-of-the-art of the deterministic placement methods, describing and comparing the different alternative methods available in the literature, and we illustrate their potential to fabricate van der Waals heterostructures, to integrate 2D materials into complex devices and to fabricate artificial bilayer structures where the layers present a user-defined rotational twisting angle. [ABSTRACT FROM AUTHOR]

Since the discovery of graphene, the family of two-dimensional materials has grown, displaying a broad range of electronic properties. Recent additions include semiconductors with spin-valley coupling, Ising superconductors that can be tuned into a quantum metal, possible Mott insulators with tunable charge-density waves, and topological semimetals with edge transport. However, no two-dimensional crystal with intrinsic magnetism has yet been discovered; such a crystal would be useful in many technologies from sensing to data storage. Theoretically, magnetic order is prohibited in the two-dimensional isotropic Heisenberg model at finite temperatures by the Mermin-Wagner theorem. Magnetic anisotropy removes this restriction, however, and enables, for instance, the occurrence of two-dimensional Ising ferromagnetism. Here we use magneto-optical Kerr effect microscopy to demonstrate that monolayer chromium triiodide (CrI3) is an Ising ferromagnet with out-of-plane spin orientation. Its Curie temperature of 45 kelvin is only slightly lower than that of the bulk crystal, 61 kelvin, which is consistent with a weak interlayer coupling. Moreover, our studies suggest a layer-dependent magnetic phase, highlighting thickness-dependent physical properties typical of van der Waals crystals. Remarkably, bilayer CrI3 displays suppressed magnetization with a metamagnetic effect, whereas in trilayer CrI3 the interlayer ferromagnetism observed in the bulk crystal is restored. This work creates opportunities for studying magnetism by harnessing the unusual features of atomically thin materials, such as electrical control for realizing magnetoelectronics, and van der Waals engineering to produce interface phenomena. [ABSTRACT FROM AUTHOR]

The integration of atomically-thin layers of two dimensional (2D) materials in nanodevices demands for precise techniques at the nanoscale permitting their local modification, structuration or resettlement. Here, we present the use of Local Oxidation Nanolithography (LON) performed with an Atomic Force Microscope (AFM) for the patterning of nanometric motifs on different metallic Transition Metal Dichalcogenides (TMDCs). We show the results of a systematic study of the parameters that affect the LON process as well as the use of two different modes of lithographic operation: dynamic and static. The application of this kind of lithography in different types of TMDCs demonstrates the versatility of the LON for the creation of accurate and reproducible nanopatterns in exfoliated 2D-crystals and reveals the influence of the chemical composition and crystalline structure of the systems on the morphology of the resultant oxide motifs. [ABSTRACT FROM AUTHOR]

In this work we report the structural and magnetic characterization of a new three-dimensional porous metal–organic framework (MOF) based on iron(iii) and the formate anion, [Fe(HCO2)3]n·nHCO2H (1), which was obtained by solvothermal synthesis. The tridimensional structure crystallizes in the trigonal space group R3̅c and is formed by highly regular octahedral Fe(OHCO)6 units. These units contain six equal Fe–O distances, with angles slightly different from 90° or 180°. The packing of 1 corresponds to a 3D covalent network defined by face sharing between the parallelepipeds, which are formed by the interactions of Fe(OHCO)6 units through formate ligands, thus generating a 41263 topology. This topology contains channels in the three spatial directions, in which it is possible to find guest molecules of formic acid. The thermogravimetric analysis shows that 1 remains stable till 180 °C; after this temperature the decomposition of 1 begins. From a magnetic point of view, the reported MOF presents an antiferromagnetic behaviour in the 296 to 20 K range. The fit of the experimental data between room temperature and 50 K, using the high temperature series model (HTS model), permits us to estimate a J value of −1.01 cm−1, which is in agreement with the reported values for analogous systems based on transition metal ions and formate ligands. Below this temperature, a weak ferromagnetism as a product of spin canting was observed due to the anti–anti coordination mode of the bridging ligand, which satisfies the requirement for Dzyaloshinsky–Moriya antisymmetric interactions between the FeIII ions. The isothermal magnetization obtained at 2 K shows that the magnetization increases linearly with the applied magnetic field, reaching a value of 0.49Nβ at the highest applied field of 50 kOe, indicating the antiferromagnetic character of the ground state. DFT calculations using a dinuclear fragment confirm the magnitude and nature of the magnetic phenomena of this extended system at high temperatures. [ABSTRACT FROM AUTHOR]

Herein, we describe the combination of polyoxometalates (POMs) with a polynuclear metallic cluster Mn4 {Mn4 = [Mn4(OAc)2(pdmH)6]2+, (pdmH = deprotonated pyridine-2,6-dimethanol; C7H8NO2)} for the construction of ionic crystals with layered architectures. Choosing a POM with the appropriate charge and size not only allows for the fine tuning of the stacking periodicity, but it also allows modifying the in-plane packing motif and density of the cationic metallic clusters. The isolation of differently layered hybrid crystals with the same Mn4 single-molecule-magnet (SMM) system allowed for the direct comparison of the magnetic properties of such materials. The variation of the slow relaxation properties of the SMM clusters may be attributed to the variability of the low-energy spin states, which are particularly sensitive to the specific counternanion used. [ABSTRACT FROM AUTHOR]

Deposition of clean and defect-free atomically thin two-dimensional crystalline flakes on surfaces by mechanical exfoliation of layered bulk materials has proven to be a powerful technique, but it requires a fast, reliable and non-destructive way to identify the atomically thin flakes among a crowd of thick flakes. In this work, we provide general guidelines to identify ultrathin flakes of TaSe by means of optical microscopy and Raman spectroscopy. Additionally, we determine the optimal substrates to facilitate the optical identification of atomically thin TaSe crystals. Experimental realization and isolation of ultrathin layers of TaSe enables future studies on the role of the dimensionality in interesting phenomena such as superconductivity and charge density waves. Graphical abstract: [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Although the coexistence of superconductivity and ferromagnetism in one compound is rare, some examples of such materials are known to exist. Methods to physically prepare hybrid structures with both competing phases are also known, which rely on the nanofabrication of alternating conducting layers. Chemical methods of building up hybrid materials with organic molecules (superconducting layers) and metal complexes (magnetic layers) have provided examples of superconductivity with some magnetic properties, but not fully ordered. Now, we report a chemical design strategy that uses the self assembly in solution of macromolecular nanosheet building blocks to engineer the coexistence of superconductivity and magnetism in [Ni0.66Al0.33(OH)2][TaS2] at ∼4 K. The method is further demonstrated in the isostructural [Ni0.66Fe0.33(OH)2][TaS2], in which the magnetic ordering is shifted from 4 K to 16 K. [ABSTRACT FROM AUTHOR]

It is demonstrated how local oxidation nanolithography performed with an atomic force microscope (AFM-LON) may be successfully employed for the nanopatterning of insulating regions of Ta2O5 on TaS2 ultrathin metallic layers. This provides a simple approach for the fabrication of electronic devices, such as single-electron transistors, at the nanoscale. [ABSTRACT FROM AUTHOR]