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Defect-free monolayers of graphene and hexagonal boron nitride were previously shown to be surprisingly permeable to thermal protons, despite being completely impenetrable to all gases. It remains untested whether small ions can permeate through the two-dimensional crystals. Here we show that mechanically exfoliated graphene and hexagonal boron nitride exhibit perfect Nernst selectivity such that only protons can permeate through, with no detectable flow of counterions. In the experiments, we used suspended monolayers that had few if any atomic-scale defects, as shown by gas permeation tests, and placed them to separate reservoirs filled with hydrochloric acid solutions. Protons accounted for all the electrical current and chloride ions were blocked. This result corroborates the previous conclusion that thermal protons can pierce defect-free two-dimensional crystals. Besides importance for theoretical developments, our results are also of interest for research on various separation technologies based on two-dimensional materials.

It has long been an aspirational goal to create artificial structures that allow fast permeation of water but reject even the smallest hydrated ions, replicating the feat achieved by nature in protein channels (e.g., aquaporins). Despite recent progress in creating nanoscale pores and capillaries, these structures still remain distinctly larger than protein channels. We report capillaries made by effectively extracting one atomic plane from bulk crystals, which leaves a two-dimensional slit of a few angstroms in height. Water moves through these capillaries with little resistance, whereas no permeation could be detected even for such small ions as Na+ and Cl-. Only protons (H+) can diffuse through monolayer water inside the capillaries. These observations improve our understanding of molecular transport at the atomic scale.

Atoms start behaving as waves rather than classical particles if confined in spaces commensurate with their de Broglie wavelength. At room temperature this length is only about one angstrom even for the lightest atom, hydrogen. This restricts quantum-confinement phenomena for atomic species to the realm of very low temperatures. Here we show that van der Waals gaps between atomic planes of layered crystals provide angstrom-size channels that make quantum confinement of protons apparent even at room temperature. Our transport measurements show that thermal protons experience a notably higher barrier than deuterons when entering van der Waals gaps in hexagonal boron nitride and molybdenum disulfide. This is attributed to the difference in de Broglie wavelength of the isotopes. Once inside the crystals, transport of both isotopes can be described by classical diffusion, albeit with unexpectedly fast rates, comparable to that of protons in water. The demonstrated angstrom-size channels can be exploited for further studies of atomistic quantum confinement and, if the technology can be scaled up, for sieving hydrogen isotopes.

It has been an ultimate but seemingly distant goal of nanofluidics to controllably fabricate capillaries with dimensions approaching the size of small ions and water molecules. We report ion transport through ultimately narrow slits that are fabricated by effectively removing a single atomic plane from a bulk crystal. The atomically flat angstrom-scale slits exhibit little surface charge, allowing elucidation of the role of steric effects. We find that ions with hydrated diameters larger than the slit size can still permeate through, albeit with reduced mobility. The confinement also leads to a notable asymmetry between anions and cations of the same diameter. Our results provide a platform for studying effects of angstrom-scale confinement, which is important for development of nanofluidics, molecular separation and other nanoscale technologies.

Graphene oxide membranes show exceptional molecular permeation properties, with a promise for many applications. However, their use in ion sieving and desalination technologies is limited by a permeation cutoff of ~9 Angstrom, which is larger than hydrated ion diameters for common salts. The cutoff is determined by the interlayer spacing d ~13.5 Angstrom, typical for graphene oxide laminates that swell in water. Achieving smaller d for the laminates immersed in water has proved to be a challenge.Here we describe how to control d by physical confinement and achieve accurate and tuneable ion sieving. Membranes with d from ~ 9.8 Angstrom to 6.4 Angstrom are demonstrated, providing the sieve size smaller than typical ions' hydrated diameters.In this regime, ion permeation is found to be thermally activated with energy barriers of ~10-100 kJ/mol depending on d. Importantly, permeation rates decrease exponentially with decreasing the sieve size but water transport is weakly affected (by a factor of <2). The latter is attributed to a low barrier for water molecules entry and large slip lengths inside graphene capillaries. Building on these findings, we demonstrate a simple scalable method to obtain graphene-based membranes with limited swelling, which exhibit 97% rejection for NaCl.

Nanometre-scale pores and capillaries have long been studied because of their importance in many natural phenomena and their use in numerous applications. A more recent development is the ability to fabricate artificial capillaries with nanometre dimensions, which has enabled new research on molecular transport and led to the emergence of nanofluidics. But surface roughness in particular makes it challenging to produce capillaries with precisely controlled dimensions at this spatial scale. Here we report the fabrication of narrow and smooth capillaries through van der Waals assembly, with atomically flat sheets at the top and bottom separated by spacers made of two-dimensional crystals with a precisely controlled number of layers. We use graphene and its multilayers as archetypal two-dimensional materials to demonstrate this technology, which produces structures that can be viewed as if individual atomic planes had been removed from a bulk crystal to leave behind flat voids of a height chosen with atomic-scale precision. Water transport through the channels, ranging in height from one to several dozen atomic planes, is characterized by unexpectedly fast flow (up to 1 metre per second) that we attribute to high capillary pressures (about 1,000 bar) and large slip lengths. For channels that accommodate only a few layers of water, the flow exhibits a marked enhancement that we associate with an increased structural order in nanoconfined water. Our work opens up an avenue to making capillaries and cavities with sizes tunable to {\aa}ngstr\"om precision, and with permeation properties further controlled through a wide choice of atomically flat materials available for channel walls.

We use ionic liquid-assisted electric field effect to tune the carrier density in an electron-doped cuprate ultrathin film and cause a two-dimensional superconductor-insulator transition (SIT). The low upper critical field in this system allows us to perform magnetic field (B)-induced SIT in the liquid-gated superconducting film. Finite-size scaling analysis indicates that SITs induced both by electric and magnetic field are quantum phase transitions and the transitions are governed by percolation effects - quantum mechanical in the former and classical in the latter case. Compared to the hole-doped cuprates, the SITs in electron-doped system occur at critical sheet resistances (Rc) much lower than the pair quantum resistance RQ=h/(2e)2=6.45 k{\Omega}, suggesting the possible existence of fermionic excitations at finite temperature at the insulating phase near SITs., Comment: Manuscript including supplementary materials

The confinement of the two dimensional electron gas (2DEG), preferential occupancy of the Ti 3d orbital and strong spin-orbit coupling at the LaAlO$_3$/SrTiO$_3$ interface play a significant role in its emerging properties. Here we report a fourfold oscillation in the anisotropic magneto resistance (AMR) and the observation of planar Hall effect (PHE) at the LaAlO$_3$/SrTiO$_3$ heterointerface. We evaluate the carrier confinement effects on the AMR and find that the fourfold oscillation appears only for the case of 2DEG system while it is twofold for the 3D system. As the fourfold oscillation fits well to the phenomenological model for a cubic symmetry system, we attribute this oscillation to the anisotropy in the magnetic scattering arising from the interaction of electrons with the localized magnetic moments coupled to the crystal symmetry. The AMR behavior is further found to be sensitive to applied gate electric field, emphasizing the significance of spin-orbit coupling at the interface. These confinement effects suggest that the magnetic interactions are predominant at the interface, and the gate electric field modulation of AMR suggest the possible gate tunable magnetic interactions in these systems. The observed large PHE further indicates that the in plane nature of magnetic ordering arises from the in-plane Ti 3dxy orbitals., Comment: Main manuscript: 20 pages, Figures: 5, Supplementary Information: 5 pages

The electronic properties of SrRuO3/LaAlO3 (SRO/LAO) superlattices with different interlayer thicknesses of SRO layers were studied. As the thickness of SRO layers is reduced, the superlattices exhibit a metal-insulator transition implying transformation into a more localized state from its original bulk metallic state. The strain effect on the metal-insulator transition was also examined. The origin of the metal-insulator transition in ultrathin SRO film is discussed. All the superlattices, even those with SRO layers as thin as 2 unit cells, are ferromagnetic at low temperatures. Moreover, we demonstrate field effect devices based on such multilayer superlattice structures., Comment: 19 pages, 5 figures, 1 table

Molybdenum disulphide, a diamagnetic layered dichalcogenide solid, is found to show magnetic ordering at room temperature when exposed to a 2 MeV proton beam. The temperature dependence of magnetization displays ferrimagnetic behavior with a Curie temperature of 895 K. A disorder mode corresponding to a zone-edge phonon and a Mo valence higher than +4, have been detected in the irradiated samples using Raman and X-ray photoelectron spectroscopy, respectively. The possible origins of long-range magnetic ordering in irradiated MoS2 samples are discussed.

The observation of a two dimensional electron gas (2DEG) (1, 2), superconductivity (3, 4), magnetic effects (5) and electronic phase separation (6-8) at the interfaces of insulating oxides, especially LaAlO3/SrTiO3, has further enhanced the potential of complex oxides for novel electronics. The occurrence of the 2DEG is strongly believed to be driven by the polarization discontinuity (9) at the interface between the two oxides. In this scenario, the crystal orientation plays an important role and no conductivity would be expected for e.g., the interface between LaAlO3 and (110)-oriented SrTiO3, which should not have a polarization discontinuity (10, 11). Here, we report the observation of unexpected conductivity at the LaAlO3/SrTiO3 interface prepared on (110)-oriented SrTiO3. The conductivity was further found to be strongly anisotropic, with the ratio of the conductance along the different directions parallel to the substrate surface showing a remarkable dependence on the oxygen pressure during deposition. The conductance and its anisotropy are discussed based on the atomic structure at the interface, as revealed by Scanning Transmission Electron Microscopy (STEM) and further supported by density functional theory (DFT) calculations., Comment: 17 pages, 5 figures

The interface between the polar LaAlO$_3$ and nonpolar SrTiO$_3$ layers has been shown to exhibit various electronic and magnetic phases such as two dimensional electron gas, superconductivity, magnetism and electronic phase separation. These rich phases are expected due to the strong interplay between charge, spin and orbital degree of freedom at the interface between these complex oxides, leading to the electronic reconstruction in this system. However, until now all of these new properties have been studied extensively based on the interfaces which involve a polar LaAlO$_3$ layer. To investigate the role of the A and B cationic sites of the ABO$_3$ polar layer, here we study various combinations of polar/nonpolar oxide (NdAlO$_3$/SrTiO$_3$, PrAlO$_3$/SrTiO$_3$ and NdGaO$_3$/SrTiO$_3$) interfaces which are similar in nature to LaAlO$_3$/SrTiO$_3$ interface. Our results show that all of these new interfaces can also produce 2DEG at their interfaces, supporting the idea that the electronic reconstruction is the driving mechanism for the creation of the 2DEG at these oxide interfaces. Furthermore, the electrical properties of these interfaces are shown to be strongly governed by the interface strain and strong correlation effects provided by the polar layers. Our observations may provide a novel approach to further tune the properties of the 2DEG at the selected polar/nonpolar oxide interfaces., Comment: 5 pages, 4 figures

The surface termination of (100)-oriented LaAlO3 (LAO) single crystals was examined by atomic force microscopy and optimized to produce a single-terminated atomically flat surface by annealing. Then the atomically flat STO film was achieved on a single-terminated LAO substrate, which is expected to be similar to the n-type interface of two-dimensional electron gas (2DEG), i.e., (LaO)-(TiO2). Particularly, that can serve as a mirror structure for the typical 2DEG heterostructure to further clarify the origin of 2DEG. This newly developed interface was determined to be highly insulating. Additionally, this study demonstrates an approach to achieve atomically flat film growth based on LAO substrates., Comment: 4 pages, 3 figures

We report on the electric-field-induced reversible metal-insulator transition (MIT) of the insulating LaAlO3 thin films observed in metal/LaAlO3/Nb-SrTiO3 heterostructures. The switching voltage depends strongly on the thickness of the LaAlO3 thin film which indicates that a minimum thickness is required for the MIT. A constant opposing voltage is required to deplete the charges from the defect states. Our experimental results exclude the possibility of diffusion of the metal electrodes or oxygen vacancies into the LaAlO3 layer. Instead, the phenomenon is attributed to the formation of a quasi-conduction band (QCB) in the defect states of LaAlO3 that forms a continuum state with the conduction band of the Nb-SrTiO3. Once this continuum (metallic) state is formed, the state remains stable even when the voltage bias is turned off. The thickness dependent reverse switch-on voltage and the constant forward switch-off voltage are consistent with our model. The viewpoint proposed here can provide an alternative mechanism for resistive switching in complex oxides., Comment: 5 pages, 4 figures

We report the optical, electrical transport, and magnetotransport properties of high quality oxygen deficient SrTiO3 (STO) single crystal film fabricated by pulsed laser deposition and reduced in the vacuum chamber. The oxygen vacancy distribution in the thin film is expected to be uniform. By comparing the electrical properties with oxygen deficient bulk STO, it was found that the oxygen vacancies in bulk STO is far from uniform over the whole material. The metal-insulator transition (MIT) observed in the oxygen deficient STO film was found to be induced by the carrier freeze-out effect. The low temperature frozen state can be re-excited by an electric field, Joule heating, and surprisingly also a large magnetic field., Comment: 5 pages, 5 figures

The use of graphene electronics in space will depend on the radiation hardness of graphene. The damage threshold of graphene samples, subjected to 2 MeV proton irradiation, was found to increase with layer number and also when the graphene layer was supported by a substrate. The thermal properties of graphene as a function of the number of layers or as influenced by the substrate argue against a thermal model for the production of damage by the ion beam. We propose a model of intense electronically-stimulated surface desorption of the atoms as the most likely process for this damage mechanism., Comment: 20 pages, 5 figures

The insulating state is one of the most basic electronic phases in condensed matter. This state is characterised by an energy gap for electronic excitations that makes an insulator electrically inert at low energy. However, for complex oxides, the very concept of an insulator must be re-examined. Complex oxides behave differently from conventional insulators such as SiO2, on which the entire semiconductor industry is based, because of the presence of multiple defect levels within their band gap. As the semiconductor industry is moving to such oxides for high-dielectric (high-k) materials, we need to truly understand the insulating properties of these oxides under various electric field excitations. Here we report a new class of material called nonlinear insulators that exhibits a reversible electric-field-induced metal-insulator transition. We demonstrate this behaviour for an insulating LaAlO3 thin film in a metal/LaAlO3/Nb-SrTiO3 heterostructure. Reproducible transitions were observed between a low-resistance metallic state and a high-resistance non-metallic state when applying suitable voltages. Our experimental results exclude the possibility that diffusion of the metal electrodes or oxygen vacancies into the LaAlO3 layer is occurring. Instead, the phenomenon is attributed to the formation of a quasi-conduction band (QCB) in the defect states of LaAlO3 that forms a continuum state with the conduction band of the Nb-SrTiO3. Once this continuum (metallic) state is formed, the state remains stable even when the voltage bias is turned off. An opposing voltage is required to deplete the charges from the defect states. Our ability to manipulate and control these defect states and, thus, the nonlinear insulating properties of complex oxides will open up a new path to develop novel devices., Comment: 23 pages, 4 figures