Molecular transport through capillaries made with atomic-scale precision.

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 ångström precision, and with permeation properties further controlled through a wide choice of atomically flat materials available for channel walls.

Large area resist-free soft lithographic patterning of graphene.

Large area low-cost patterning is a challenging problem in graphene research. A resist-free, single-step, large area and cost effective soft lithographic patterning strategy is presented for graphene. The technique is applicable on any arbitrary substrate that needs to be covered with a graphene film and provides a viable route to large-area patterning of graphene for device applications.

Metal-insulator transition in SrTiO(3-x) thin films induced by frozen-out carriers.

We report optical, electrical and magnetotransport properties of oxygen deficient SrTiO(3) (SrTiO(3-x)) thin films fabricated by pulsed laser deposition technique. The oxygen vacancies (O(vac)) in the thin film are expected to be uniform. By comparing its electrical properties to those of bulk SrTiO(3-x), it was found that O(vac) in bulk SrTiO(3-x) is far from uniform over the whole material. The metal-insulator transition (MIT) observed in the SrTiO(3-x) film was found to be induced by the carrier freeze-out effect. The low temperature frozen state can be reexcited by Joule heating, electric and intriguingly magnetic field.

Perfect proton selectivity in ion transport through two-dimensional crystals.

Defect-free monolayers of graphene and hexagonal boron nitride are 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 use suspended monolayers that have few, if any, atomic-scale defects, as shown by gas permeation tests, and place them to separate reservoirs filled with hydrochloric acid solutions. Protons account for all the electrical current and chloride ions are blocked. This result corroborates the previous conclusion that thermal protons can pierce defect-free two-dimensional crystals. Besides the importance for theoretical developments, our results are also of interest for research on various separation technologies based on two-dimensional materials.

Complete steric exclusion of ions and proton transport through confined monolayer water.

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.

Transport of hydrogen isotopes through interlayer spacing in van der Waals crystals.

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 ångström even for the lightest atom, hydrogen. This restricts quantum-confinement phenomena for atomic species to the realm of very low temperatures1-5. Here, we show that van der Waals gaps between atomic planes of layered crystals provide ångström-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 the de Broglie wavelengths 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 ångström-size channels can be exploited for further studies of atomistic quantum confinement and, if the technology can be scaled up, for sieving hydrogen isotopes.

Size effect in ion transport through angstrom-scale slits.

In the field of nanofluidics, it has been an ultimate but seemingly distant goal 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 the effects of angstrom-scale confinement, which is important for the development of nanofluidics, molecular separation, and other nanoscale technologies.

Long-range magnetic coupling across a polar insulating layer.

Magnetic interactions in solids are normally mediated by short-range exchange or weak dipole fields. Here we report a magnetic interaction that can propagate over long distances (∼10 nm) across a polar insulating oxide spacer. Evidence includes oscillations of magnetization, coercivity and field-cooled loop shift with the thickness of LaAlO3 in La0.67Sr0.33MnO3/LaAlO3/SrTiO3 heterostructures. Similar modifications of the hysteresis loop appear when two coupled films of La0.67Sr0.33MnO3 are separated by LaAlO3, or another polar insulator, but they are absent when the oxide spacer layer is nonpolar. The loop shift is attributed to strong spin-orbit coupling and Dzyaloshinskii-Moriya interaction at the interfaces. There is evidence from inelastic light scattering that the polar spacer mediates long-range transmission of orbital magnetization. This coupling mechanism is expected to apply for any conducting ferromagnetic oxide with mixed valence; in view of electron hopping frequency involved, it raises the prospect of terahertz tunability of magnetic coupling.

Black Phosphorus Transistors with Near Band Edge Contact Schottky Barrier.

Black phosphorus (BP) is a new class of 2D material which holds promise for next generation transistor applications owing to its intrinsically superior carrier mobility properties. Among other issues, achieving good ohmic contacts with low source-drain parasitic resistance in BP field-effect transistors (FET) remains a challenge. For the first time, we report a new contact technology that employs the use of high work function nickel (Ni) and thermal anneal to produce a metal alloy that effectively reduces the contact Schottky barrier height (ΦB) in a BP FET. When annealed at 300 °C, the Ni electrode was found to react with the underlying BP crystal and resulted in the formation of nickel-phosphide (Ni2P) alloy. This serves to de-pin the metal Fermi level close to the valence band edge and realizes a record low hole ΦB of merely ~12 meV. The ΦB at the valence band has also been shown to be thickness-dependent, wherein increasing BP multi-layers results in a smaller ΦB due to bandgap energy shrinkage. The integration of hafnium-dioxide high-k gate dielectric additionally enables a significantly improved subthreshold swing (SS ~ 200 mV/dec), surpassing previously reported BP FETs with conventional SiO2 gate dielectric (SS > 1 V/dec).

Unexpected observation of spatially separated Kondo scattering and ferromagnetism in Ta alloyed anatase TiO2 thin films.

We report the observation of spatially separated Kondo scattering and ferromagnetism in anatase Ta0.06Ti0.94O2 thin films as a function of thickness (10-200 nm). The Kondo behavior observed in thicker films is suppressed on decreasing thickness and vanishes below ~25 nm. In 200 nm film, transport data could be fitted to a renormalization group theory for Kondo scattering though the carrier density in this system is lower by two orders of magnitude, the magnetic entity concentration is larger by a similar magnitude and there is strong electronic correlation compared to a conventional system such as Cu with magnetic impurities. However, ferromagnetism is observed at all thicknesses with magnetic moment per unit thickness decreasing beyond 10 nm film thickness. The simultaneous presence of Kondo and ferromagnetism is explained by the spatial variation of defects from the interface to surface which results in a dominantly ferromagnetic region closer to substrate-film interface while the Kondo scattering is dominant near the surface and decreasing towards the interface. This material system enables us to study the effect of neighboring presence of two competing magnetic phenomena and the possibility for tuning them.

Anisotropic two-dimensional electron gas at the LaAlO3/SrTiO3 (110) interface.

The observation of a high-mobility two-dimensional electron gas between two insulating complex oxides, especially LaAlO3/SrTiO3, has enhanced the potential of oxides for electronics. The occurrence of this conductivity is believed to be driven by polarization discontinuity, leading to an electronic reconstruction. In this scenario, the crystal orientation has an important role and no conductivity would be expected, for example, for the interface between LaAlO3 and (110)-oriented SrTiO3, which should not have a polarization discontinuity. Here we report the observation of unexpected conductivity at the LaAlO3/SrTiO3 interface prepared on (110)-oriented SrTiO3, with a LaAlO3-layer thickness-dependent metal-insulator transition. Density functional theory calculation reveals that electronic reconstruction, and thus conductivity, is still possible at this (110) interface by considering the energetically favourable (110) interface structure, that is, buckled TiO2/LaO, in which the polarization discontinuity is still present. The conductivity was further found to be strongly anisotropic along the different crystallographic directions with potential for anisotropic superconductivity and magnetism, leading to possible new physics and applications.