Combining Freestanding Ferroelectric Perovskite Oxides with Two-Dimensional Semiconductors for High Performance Transistors.

We demonstrate the fabrication of field-effect transistors based on single-layer MoS2 and a thin layer of BaTiO3 (BTO) dielectric, isolated from its parent epitaxial template substrate. Thin BTO provides an ultrahigh-κ gate dielectric effectively screening Coulomb scattering centers. These devices show mobilities substantially larger than those obtained with standard SiO2 dielectrics and comparable with values obtained with hexagonal boron nitride, a dielectric employed for fabrication of high-performance two-dimensional (2D) based devices. Moreover, the ferroelectric character of BTO induces a robust hysteresis of the current vs gate voltage characteristics, attributed to its polarization switching. This hysteresis is strongly suppressed when the device is warmed up above the tetragonal-to-cubic transition temperature of BTO that leads to a ferroelectric-to-paraelectric transition. This hysteretic behavior is attractive for applications in memory storage devices. Our results open the door to the integration of a large family of complex oxides exhibiting strongly correlated physics in 2D-based devices.

Linear Magnetoelectric Phase in Ultrathin MnPS_{3} Probed by Optical Second Harmonic Generation.

The transition metal thiophosphates MPS_{3} (M=Mn, Fe, Ni) are a class of van der Waals stacked insulating antiferromagnets that can be exfoliated down to the ultrathin limit. MnPS_{3} is particularly interesting because its Néel ordered state breaks both spatial-inversion and time-reversal symmetries, allowing for a linear magnetoelectric phase that is rare among van der Waals materials. However, it is unknown whether this unique magnetic structure of bulk MnPS_{3} remains stable in the ultrathin limit. Using optical second harmonic generation rotational anisotropy, we show that long-range linear magnetoelectric type Néel order in MnPS_{3} persists down to at least 5.3 nm thickness. However an unusual mirror symmetry breaking develops in ultrathin samples on SiO_{2} substrates that is absent in bulk materials, which is likely related to substrate induced strain.

Interaction-Driven Giant Orbital Magnetic Moments in Carbon Nanotubes.

Carbon nanotubes continue to be model systems for studies of confinement and interactions. This is particularly true in the case of so-called "ultraclean" carbon nanotube devices offering the study of quantum dots with extremely low disorder. The quality of such systems, however, has increasingly revealed glaring discrepancies between experiment and theory. Here, we address the outstanding anomaly of exceptionally large orbital magnetic moments in carbon nanotube quantum dots. We perform low temperature magnetotransport measurements of the orbital magnetic moment and find it is up to 7 times larger than expected from the conventional semiclassical model. Moreover, the magnitude of the magnetic moment monotonically drops with the addition of each electron to the quantum dot directly contradicting the widely accepted shell filling picture of single-particle levels. We carry out quasiparticle calculations, both from first principles and within the effective-mass approximation, and find the giant magnetic moments can only be captured by considering a self-energy correction to the electronic band structure due to electron-electron interactions.

Proximity-Induced Shiba States in a Molecular Junction.

Superconductors containing magnetic impurities exhibit intriguing phenomena derived from the competition between Cooper pairing and Kondo screening. At the heart of this competition are the Yu-Shiba-Rusinov (Shiba) states which arise from the pair breaking effects a magnetic impurity has on a superconducting host. Hybrid superconductor-molecular junctions offer unique access to these states but the added complexity in fabricating such devices has kept their exploration to a minimum. Here, we report on the successful integration of a model spin 1/2 impurity, in the form of a neutral and stable all organic radical molecule, in proximity-induced superconducting break junctions. Our measurements reveal excitations which are characteristic of a spin-induced Shiba state due to the radical's unpaired spin strongly coupled to a superconductor. By virtue of a variable molecule-electrode coupling, we access both the singlet and doublet ground states of the hybrid system which give rise to the doublet and singlet Shiba excited states, respectively. Our results show that Shiba states are a robust feature of the interaction between a paramagnetic impurity and a proximity-induced superconductor where the excited state is mediated by correlated electron-hole (Andreev) pairs instead of Cooper pairs.

Characterization of highly crystalline lead iodide nanosheets prepared by room-temperature solution processing.

Two-dimensional (2D) semiconducting materials are particularly appealing for many applications. Although theory predicts a large number of 2D materials, experimentally only a few of these materials have been identified and characterized comprehensively in the ultrathin limit. Lead iodide, which belongs to the transition metal halides family and has a direct bandgap in the visible spectrum, has been known for a long time and has been well characterized in its bulk form. Nevertheless, studies of this material in the nanometer thickness regime are rather scarce. In this article we demonstrate an easy way to synthesize ultrathin, highly crystalline flakes of PbI2 by precipitation from a solution in water. We thoroughly characterize the produced thin flakes with different techniques ranging from optical and Raman spectroscopy to temperature-dependent photoluminescence and electron microscopy. We compare the results to ab initio calculations of the band structure of the material. Finally, we fabricate photodetectors based on PbI2 and study their optoelectronic properties.

Photocurrent generation with two-dimensional van der Waals semiconductors.

Two-dimensional (2D) materials have attracted a great deal of interest in recent years. This family of materials allows for the realization of versatile electronic devices and holds promise for next-generation (opto)electronics. Their electronic properties strongly depend on the number of layers, making them interesting from a fundamental standpoint. For electronic applications, semiconducting 2D materials benefit from sizable mobilities and large on/off ratios, due to the large modulation achievable via the gate field-effect. Moreover, being mechanically strong and flexible, these materials can withstand large strain (>10%) before rupture, making them interesting for strain engineering and flexible devices. Even in their single layer form, semiconducting 2D materials have demonstrated efficient light absorption, enabling large responsivity in photodetectors. Therefore, semiconducting layered 2D materials are strong candidates for optoelectronic applications, especially for photodetection. Here, we review the state-of-the-art in photodetectors based on semiconducting 2D materials, focusing on the transition metal dichalcogenides, novel van der Waals materials, black phosphorus, and heterostructures.

Tailoring 10 nm scale suspended graphene junctions and quantum dots.

The possibility to make 10 nm scale, and low-disorder, suspended graphene devices would open up many possibilities to study and make use of strongly coupled quantum electronics, quantum mechanics, and optics. We present a versatile method, based on the electromigration of gold-on-graphene bow-tie bridges, to fabricate low-disorder suspended graphene junctions and quantum dots with lengths ranging from 6 nm up to 55 nm. We control the length of the junctions, and shape of their gold contacts by adjusting the power at which the electromigration process is allowed to avalanche. Using carefully engineered gold contacts and a nonuniform downward electrostatic force, we can controllably tear the width of suspended graphene channels from over 100 nm down to 27 nm. We demonstrate that this lateral confinement creates high-quality suspended quantum dots. This fabrication method could be extended to other two-dimensional materials.

A back-to-back diode model applied to van der Waals Schottky diodes.

The use of metal and semimetal van der Waals contacts for 2D semiconducting devices has led to remarkable device optimizations. In comparison with conventional thin-film metal deposition, a reduction in Fermi level pinning at the contact interface for van der Waals contacts results in, generally, lower contact resistances and higher mobilities. Van der Waals contacts also lead to Schottky barriers that follow the Schottky-Mott rule, allowing barrier estimates on material properties alone. In this study, we present a double Schottky barrier model and apply it to a barrier tunable all van der Waals transistor. In a molybdenum disulfide (MoS2) transistor with graphene and few-layer graphene contacts, we find that the model can be applied to extract Schottky barrier heights that agree with the Schottky-Mott rule from simple two-terminal current-voltage measurements at room temperature. Furthermore, we show tunability of the Schottky barrierin-situusing a regional contact gate. Our results highlight the utility of a basic back-to-back diode model in extracting device characteristics in all van der Waals transistors.

Improving the conductivity of graphite-based films by rapid laser annealing.

We present a method to anneal devices based on graphite films on paper and polycarbonate substrates. The devices are created using four different methods: spray-on films, graphite pencil-drawn films, liquid-phase exfoliated graphite films, and graphite powder abrasion-applied films. We characterize the optical properties of the films before and after laser annealing and report the two-terminal resistance of the devices for increased laser power density. We find the greatest improvement (16× reduction) in the resistance of spray-on film devices starting from 25.0 kΩ and reaching 1.6 kΩ at the highest annealing power densities. These improvements are attributed to local laser ablation of binders, stabilizers, and solvent residues left in the film after fabrication. This work highlights the utility of focused laser annealing for spray-on, drawn, printed, and abrasion fabricated films on substrates sensitive to heat/thermal treatments.

Universal image segmentation for optical identification of 2D materials.

Machine learning methods are changing the way data is analyzed. One of the most powerful and widespread applications of these techniques is in image segmentation wherein disparate objects of a digital image are partitioned and classified. Here we present an image segmentation program incorporating a series of unsupervised clustering algorithms for the automatic thickness identification of two-dimensional materials from digital optical microscopy images. The program identifies mono- and few-layer flakes of a variety of materials on both opaque and transparent substrates with a pixel accuracy of roughly 95%. Contrasting with previous attempts, application generality is achieved through preservation and analysis of all three digital color channels and Gaussian mixture model fits to arbitrarily shaped data clusters. Our results provide a facile implementation of data clustering for the universal, automatic identification of two-dimensional materials exfoliated onto any substrate.

Giant modulation of the electronic band gap of carbon nanotubes by dielectric screening.

Carbon nanotubes (CNTs) are a promising material for high-performance electronics beyond silicon. But unlike silicon, the nature of the transport band gap in CNTs is not fully understood. The transport gap in CNTs is predicted to be strongly driven by electron-electron (e-e) interactions and correlations, even at room temperature. Here, we use dielectric liquids to screen e-e interactions in individual suspended ultra-clean CNTs. Using multiple techniques, the transport gap is measured as dielectric screening is increased. Changing the dielectric environment from air to isopropanol, we observe a 25% reduction in the transport gap of semiconducting CNTs, and a 32% reduction in the band gap of narrow-gap CNTs. Additional measurements are reported in dielectric oils. Our results elucidate the nature of the transport gap in CNTs, and show that dielectric environment offers a mechanism for significant control over the transport band gap.

Franckeite as a naturally occurring van der Waals heterostructure.

The fabrication of van der Waals heterostructures, artificial materials assembled by individual stacking of 2D layers, is among the most promising directions in 2D materials research. Until now, the most widespread approach to stack 2D layers relies on deterministic placement methods, which are cumbersome and tend to suffer from poor control over the lattice orientations and the presence of unwanted interlayer adsorbates. Here, we present a different approach to fabricate ultrathin heterostructures by exfoliation of bulk franckeite which is a naturally occurring and air stable van der Waals heterostructure (composed of alternating SnS2-like and PbS-like layers stacked on top of each other). Presenting both an attractive narrow bandgap (<0.7 eV) and p-type doping, we find that the material can be exfoliated both mechanically and chemically down to few-layer thicknesses. We present extensive theoretical and experimental characterizations of the material's electronic properties and crystal structure, and explore applications for near-infrared photodetectors.

Precise and reversible band gap tuning in single-layer MoSe2 by uniaxial strain.

We present photoluminescence (PL) spectroscopy measurements of single-layer MoSe2 as a function of uniform uniaxial strain. A simple clamping and bending method is described that allows for application of uniaxial strain to layered, 2D materials with strains up to 1.1% without slippage. Using this technique, we find that the electronic band gap of single layer MoSe2 can be reversibly tuned by -27 ± 2 meV per percent of strain. This is in agreement with our density-functional theory calculations, which estimate a modulation of -32 meV per percent of strain, taking into account the role of deformation of the underlying substrate upon bending. Finally, due to its narrow PL spectra as compared with that of MoS2, we show that MoSe2 provides a more precise determination of small changes in strain making it the ideal 2D material for strain applications.

Sequential Electron Transport and Vibrational Excitations in an Organic Molecule Coupled to Few-Layer Graphene Electrodes.

Graphene electrodes are promising candidates to improve reproducibility and stability in molecular electronics through new electrode-molecule anchoring strategies. Here we report sequential electron transport in few-layer graphene transistors containing individual curcuminoid-based molecules anchored to the electrodes via π-π orbital bonding. We show the coexistence of inelastic co-tunneling excitations with single-electron transport physics due to an intermediate molecule-electrode coupling; we argue that an intermediate electron-phonon coupling is the origin of these vibrational-assisted excitations. These experimental observations are complemented with density functional theory calculations to model electron transport and the interaction between electrons and vibrational modes of the curcuminoid molecule. We find that the calculated vibrational modes of the molecule are in agreement with the experimentally observed excitations.

Titanium trisulfide (TiS3): a 2D semiconductor with quasi-1D optical and electronic properties.

We present characterizations of few-layer titanium trisulfide (TiS3) flakes which, due to their reduced in-plane structural symmetry, display strong anisotropy in their electrical and optical properties. Exfoliated few-layer flakes show marked anisotropy of their in-plane mobilities reaching ratios as high as 7.6 at low temperatures. Based on the preferential growth axis of TiS3 nanoribbons, we develop a simple method to identify the in-plane crystalline axes of exfoliated few-layer flakes through angle resolved polarization Raman spectroscopy. Optical transmission measurements show that TiS3 flakes display strong linear dichroism with a magnitude (transmission ratios up to 30) much greater than that observed for other anisotropic two-dimensional (2D) materials. Finally, we calculate the absorption and transmittance spectra of TiS3 in the random-phase-approximation (RPA) and find that the calculations are in qualitative agreement with the observed experimental optical transmittance.

Enhanced superconductivity in atomically thin TaS2.

The ability to exfoliate layered materials down to the single layer limit has presented the opportunity to understand how a gradual reduction in dimensionality affects the properties of bulk materials. Here we use this top-down approach to address the problem of superconductivity in the two-dimensional limit. The transport properties of electronic devices based on 2H tantalum disulfide flakes of different thicknesses are presented. We observe that superconductivity persists down to the thinnest layer investigated (3.5 nm), and interestingly, we find a pronounced enhancement in the critical temperature from 0.5 to 2.2 K as the layers are thinned down. In addition, we propose a tight-binding model, which allows us to attribute this phenomenon to an enhancement of the effective electron-phonon coupling constant. This work provides evidence that reducing the dimensionality can strengthen superconductivity as opposed to the weakening effect that has been reported in other 2D materials so far.

Temperature-Dependent Raman Spectroscopy of Titanium Trisulfide (TiS3) Nanoribbons and Nanosheets.

Titanium trisulfide (TiS3) has recently attracted the interest of the 2D community because it presents a direct bandgap of ∼1.0 eV, shows remarkable photoresponse, and has a predicted carrier mobility up to 10000 cm(2) V(-1) s(-1). However, a study of the vibrational properties of TiS3, relevant to understanding the electron-phonon interaction that can be the main mechanism limiting the charge carrier mobility, is still lacking. In this work, we take the first steps to study the vibrational properties of TiS3 through temperature-dependent Raman spectroscopy measurements of TiS3 nanoribbons and nanosheets. Our investigation shows that all the Raman modes linearly soften (red shift) as the temperature increases from 88 to 570 K due to anharmonic vibrations of the lattice, which also includes contributions from the lattice thermal expansion. This softening with the temperature of the TiS3 modes is more pronounced than that observed in other 2D semiconductors, such as MoS2, MoSe2, WSe2, and black phosphorus (BP). This marked temperature dependence of the Raman spectra could be exploited to determine the temperature of TiS3 nanodevices by using Raman spectroscopy as a noninvasive and local thermal probe. Interestingly, the TiS3 nanosheets show a stronger temperature dependence of the Raman modes than the nanoribbons, which we attribute to lower interlayer coupling in the nanosheets.

TiS3 transistors with tailored morphology and electrical properties.

Control over the morphology of TiS3 is demonstrated by synthesizing 1D nanoribbons and 2D nanosheets. The nanosheets can be exfoliated down to a single layer. Through extensive characterization of the two morphologies, differences in the electronic properties are found and attributed to a higher density of sulphur vacancies in nanosheets, which, according to density functional theory calculations, leads to an n-type doping.