Molecular-Beam Epitaxy of Two-Dimensional In2Se3 and Its Giant Electroresistance Switching in Ferroresistive Memory Junction.

Ferroelectric thin film has attracted great interest for nonvolatile memory applications and can be used in either ferroelectric Schottky diodes or ferroelectric tunneling junctions due to its promise of fast switching speed, high on-to-off ratio, and nondestructive readout. Two-dimensional α-phase indium selenide (In2Se3), which has a modest band gap and robust ferroelectric properties stabilized by dipole locking, is an excellent candidate for multidirectional piezoelectric and switchable photodiode applications. However, the large-scale synthesis of this material is still elusive, and its performance as a ferroresistive memory junction is rarely reported. Here, we report the low-temperature molecular-beam epitaxy (MBE) of large-area monolayer α-In2Se3 on graphene and demonstrate the use of α-In2Se3 on graphene in ferroelectric Schottky diode junctions by employing high-work-function gold as the top electrode. The polarization-modulated Schottky barrier formed at the interface exhibits a giant electroresistance ratio of 3.9 × 106 with a readout current density of >12 A/cm2, which is more than 200% higher than the state-of-the-art technology. Our MBE growth method allows a high-quality ultrathin film of In2Se3 to be heteroepitaxially grown on graphene, thereby simplifying the fabrication of high-performance 2D ferroelectric junctions for ferroresistive memory applications.

Substoichiometric Molybdenum Sulfide Phases with Catalytically Active Basal Planes.

Molybdenum sulfide (MoS2) is widely recognized for its catalytic activities where the edges of the crystals turn over reactions. Generating sulfur defects on the basal plane of MoS2 can improve its catalytic activity, but generally, there is a lack of model systems for understanding metal-centered catalysis on the basal planes. Here, we synthesized a new phase of substoichiometric molybdenum sulfide (s-MoSx) on a sulfur-enriched copper substrate. The basal plane of s-MoSx contains chemically reactive Mo-rich sites that can undergo dynamic dissociative adsorption/desorption processes with molecular hydrogen, thus demonstrating its usefulness for hydrogen-transfer catalysis. In addition, scanning tunneling microscopy was used to monitor surface-directed Ullmann coupling of 2,8-dibromo-dibenzothiophene molecules on s-MoSx nanosheets, where the 4-fold symmetric surface sites on s-MoSx direct C-C coupling to form cyclic tetramers with high selectivity.

Direct Bandgap-like Strong Photoluminescence from Twisted Multilayer MoS2 Grown on SrTiO3.

While direct bandgap monolayer 2D transition metal dichalcogenides (TMDs) have emerged as an important optoelectronic material due to strong light-matter interactions, their multilayer counterparts exhibit an indirect bandgap resulting in poor photon emission quantum yield. We report strong direct bandgap-like photoluminescence at ∼1.9 eV from multilayer MoS2 grown on SrTiO3, whose intensity is significantly higher than that observed in multilayer MoS2/SiO2. Using high-resolution electron microscopy we observe interlayer twist and >8% increase in the van der Waals gap, which leads to weaker interlayer coupling. This affects the evolution of the band structure in multilayer MoS2 as probed by transient absorption spectroscopy, causing higher photo carrier recombination at the direct gap. Our results provide a platform that could enable multilayer TMDs for robust optical device applications.

Polaronic Trions at the MoS2 /SrTiO3 Interface.

The reduced electrical screening in 2D materials provides an ideal platform for realization of exotic quasiparticles, that are robust and whose functionalities can be exploited for future electronic, optoelectronic, and valleytronic applications. Recent examples include an interlayer exciton, where an electron from one layer binds with a hole from another, and a Holstein polaron, formed by an electron dressed by a sea of phonons. Here, a new quasiparticle is reported, "polaronic trion" in a heterostructure of MoS2 /SrTiO3 (STO). This emerges as the Fröhlich bound state of the trion in the atomically thin monolayer of MoS2 and the very unique low energy soft phonon mode (≤7 meV, which is temperature and field tunable) in the quantum paraelectric substrate STO, arising below its structural antiferrodistortive (AFD) phase transition temperature. This dressing of the trion with soft phonons manifests in an anomalous temperature dependence of photoluminescence emission leading to a huge enhancement of the trion binding energy (≈70 meV). The soft phonons in STO are sensitive to electric field, which enables field control of the interfacial trion-phonon coupling and resultant polaronic trion binding energy. Polaronic trions could provide a platform to realize quasiparticle-based tunable optoelectronic applications driven by many body effects.

Temperature- and Phase-Dependent Phonon Renormalization in 1T'-MoS2.

Polymorph engineering of 2H-MoS2, which can be achieved by alkali metal intercalation to obtain either the mixed 2H/1T' phases or a homogeneous 1T' phase, has received wide interest recently, since this serves as an effective route to tune the electrical and catalytic properties of MoS2. As opposed to an idealized single crystal-to-single crystal phase conversion, the 2H to 1T' phase conversion results in crystal domain size reduction as well as strained lattices, although how these develop with composition is not well understood. Herein, the evolution of the phonon modes in Li-intercalated 1T'-MoS2 (Li xMoS2) are investigated as a function of different 1T'-2H compositions. We observed that the strain evolution in the mixed phases is revealed by the softening of four Raman modes, Bg ( J1), Ag ( J3), E12g, and A1g, with increasing 1T' phase composition. Additionally, the first-order temperature coefficients of the 1T' phonon mode vary linearly with increasing 1T' composition, which is explained by increased electron-phonon and strain-phonon coupling.

Molecular Beam Epitaxy of Highly Crystalline MoSe2 on Hexagonal Boron Nitride.

Molybdenum diselenide (MoSe2) is a promising two-dimensional material for next-generation electronics and optoelectronics. However, its application has been hindered by a lack of large-scale synthesis. Although chemical vapor deposition (CVD) using laboratory furnaces has been applied to grow two-dimensional (2D) MoSe2 cystals, no continuous film over macroscopically large area has been produced due to the lack of uniform control in these systems. Here, we investigate the molecular beam epitaxy (MBE) of 2D MoSe2 on hexagonal boron nitride (hBN) substrate, where highly crystalline MoSe2 film can be grown with electron mobility ∼15 cm2/(V s). Scanning transmission electron microscopy (STEM) shows that MoSe2 grains grown at an optimum temperature of 500 °C are highly oriented and coalesced to form continuous film with predominantly mirror twin boundaries. Our work suggests that van der Waals epitaxy of 2D materials is tolerant of lattice mismatch but is facilitated by substrates with similar symmetry.

Stable Molecular Diodes Based on π-π Interactions of the Molecular Frontier Orbitals with Graphene Electrodes.

In molecular electronics, it is important to control the strength of the molecule-electrode interaction to balance the trade-off between electronic coupling strength and broadening of the molecular frontier orbitals: too strong coupling results in severe broadening of the molecular orbitals while the molecular orbitals cannot follow the changes in the Fermi levels under applied bias when the coupling is too weak. Here, a platform based on graphene bottom electrodes to which molecules can bind via π-π interactions is reported. These interactions are strong enough to induce electronic function (rectification) while minimizing broadening of the molecular frontier orbitals. Molecular tunnel junctions are fabricated based on self-assembled monolayers (SAMs) of Fc(CH2 )11 X (Fc = ferrocenyl, X = NH2 , Br, or H) on graphene bottom electrodes contacted to eutectic alloy of gallium and indium top electrodes. The Fc units interact more strongly with graphene than the X units resulting in SAMs with the Fc at the bottom of the SAM. The molecular diodes perform well with rectification ratios of 30-40, and they are stable against bias stressing under ambient conditions. Thus, tunnel junctions based on graphene with π-π molecule-electrode coupling are promising platforms to fabricate stable and well-performing molecular diodes.

Quasi-Monolayer Black Phosphorus with High Mobility and Air Stability.

Black phosphorus (BP) exhibits thickness-dependent band gap and high electronic mobility. The chemical intercalation of BP with alkali metal has attracted attention recently due to the generation of universal superconductivity regardless of the type of alkali metals. However, both ultrathin BP, as well as alkali metal-intercalated BP, are highly unstable and corrode rapidly under ambient conditions. This study demonstrates that alkali metal hydride intercalation decouples monolayer to few layers BP from the bulk BP, allowing an optical gap of ≈1.7 eV and an electronic gap of 1.98 eV to be measured by photoluminescence and electron energy loss spectroscopy at the intercalated regions. Raman and transport measurements confirm that chemically intercalated BP exhibits enhanced stability, while maintaining a high hole mobility of up to ≈800 cm2 V-1 s-1 and on/off ratio exceeding 103 . The use of alkali metal hydrides as intercalants should be applicable to a wide range of layered 2D materials and pave the way for generating highly stable, quasi-monolayer 2D materials.