Robust Behavior of Charge Density Wave Quantum Motif Star-of-David in 2D NbSe2 Nanocrystals.

Charge density wave (CDW) is a typical collective phenomenon, and the phase change is generally accompanied by electronic transition with potential device applications. For the continuous miniaturization of devices, it is important to investigate the size effect down to the nanoscale. In this work, single-layer (SL) 1T-NbSe2 islands provide an ideal research platform to investigate the size effect on CDW arrangement and electronic states. The CDW motifs (Star-of-David [SOD]) at the island border are along the edge, and those at the interior tend to arrange in a triangular lattice for islands as small as 5 nm. Interestingly, in some small islands, the SOD clusters rearrange into a square-like lattice, and each SOD cluster remains robust as a quantum motif, both in the sense of geometry and electronic structures. Moreover, the electronic structure at the center of the small islands is downwards shifted compared to the big islands, explained by the spatial extension of the band bending originating from the edge of the islands. These findings reveal the robust behavior of CDW motifs down to the nanoscale and provide new insights into the size-limiting effect on 2D2D CDW ordering and electronic states down to a few nanometer extremes.

Nanoscale Control of One-Dimensional Confined States in Strongly Correlated Homojunctions.

Construction of lateral junctions is essential to generate one-dimensional (1D) confined potentials that can effectively trap quasiparticles. A series of remarkable electronic phases in one dimension, such as Wigner crystallization, are expected to be realized in such junctions. Here, we demonstrate that we can precisely tune the 1D-confined potential with an in situ manipulation technique, thus providing a dynamic way to modify the correlated electronic states at the junctions. We confirm the existence of 1D-confined potential at the homojunction of two single-layer 1T-NbSe2 islands. Such potential is structurally sensitive and shows a nonmonotonic function of their interspacing. Moreover, there is a change of electronic properties from the correlated insulator to the generalized 1D Wigner crystallization while the confinement becomes strong. Our findings not only establish the capability to fabricate structures with dynamically tunable properties, but also pave the way toward more exotic correlated systems in low dimensions.

Quantum spin liquid signatures in monolayer 1T-NbSe2.

Quantum spin liquids (QSLs) are in a quantum disordered state that is highly entangled and has fractional excitations. As a highly sought-after state of matter, QSLs were predicted to host spinon excitations and to arise in frustrated spin systems with large quantum fluctuations. Here we report on the experimental observation and theoretical modeling of QSL signatures in monolayer 1T-NbSe2, which is a newly emerging two-dimensional material that exhibits both charge-density-wave (CDW) and correlated insulating behaviors. By using scanning tunneling microscopy and spectroscopy (STM/STS), we confirm the presence of spin fluctuations in monolayer 1T-NbSe2 by observing the Kondo resonance as monolayer 1T-NbSe2 interacts with metallic monolayer 1H-NbSe2. Subsequent STM/STS imaging of monolayer 1T-NbSe2 at the Hubbard band energy further reveals a long-wavelength charge modulation, in agreement with the spinon modulation expected for QSLs. By depositing manganese-phthalocyanine (MnPc) molecules with spin S = 3/2 onto monolayer 1T-NbSe2, new STS resonance peaks emerge at the Hubbard band edges of monolayer 1T-NbSe2. This observation is consistent with the spinon Kondo effect induced by a S = 3/2 magnetic impurity embedded in a QSL. Taken together, these experimental observations indicate that monolayer 1T-NbSe2 is a new promising QSL material.

Observation of Two-Dimensional Type-II Superconductivity in Bulk 3R-TaSe2 by Scanning Tunneling Spectroscopy.

Here we report a low-temperature and vector-magnetic-field scanning tunneling microscopy/spectroscopy (STM/S) study on 3R-TaSe2. The sample surface was obtained by exfoliating a bulk 3R-TaSe2 single crystal in an ultrahigh-vacuum (UHV) chamber and then transferred in situ to STM. It was observed that the topmost layer shows a 3 × 3 charge density wave pattern at T = 4.2 K with metallic character in STS. The electronic characterization study by variable-temperature and magnetic field STS revealed that 3R-TaSe2 behaves as a type-II superconductor. More intriguingly, such superconductivity (SC) can survive under strong in-plane magnetic fields even up to 2.5 T and out-of-plane magnetic fields up to 0.7 T, exhibiting an anisotropic superconducting property. Temperature-dependent STS showed that 3R-TaSe2 undergoes a transition above 0.58 K. Our results may be important for understanding the intriguing SC properties of the 3R-phase van der Waals materials.

Ullmann-Like Covalent Bond Coupling without Participation of Metal Atoms.

Ullmann-like on-surface synthesis is one of the most appropriate approaches for the bottom-up fabrication of covalent organic nanostructures and many successes have been achieved. The Ullmann reaction requires the oxidative addition of a catalyst (a metal atom in most cases): the metal atom will insert into a carbon-halogen bond, forming organometallic intermediates, which are then reductively eliminated and form C-C covalent bonds. As a result, traditional Ullmann coupling involves reactions of multiple steps, making it difficult to control the final product. Moreover, forming the organometallic intermediates will potentially poison the metal surface catalytic reactivity. In the study, we used the 2D hBN, an atomically thin sp2-hybridized sheet with a large band gap, to protect the Rh(111) metal surface. It is an ideal 2D platform to decouple the molecular precursor from the Rh(111) surface while maintaining the reactivity of Rh(111). We realize an Ullmann-like coupling of a planar biphenylene-based molecule, i.e., 1,8-dibromobiphenylene (BPBr2), on an hBN/Rh(111) surface with an ultrahigh selectivity of the biphenylene dimer product, containing 4-, 6-, and 8-membered rings. The reaction mechanism, including electron wave penetration and the template effect of the hBN, is elucidated by combining low-temperature scanning tunneling microscopy and density functional theory calculations. Our findings are expected to play an essential role regarding the high-yield fabrication of functional nanostructures for future information devices.

Visualization of Confined Electrons at Grain Boundaries in a Monolayer Charge-Density-Wave Metal.

1D grain boundaries in transition metal dichalcogenides (TMDs) are ideal for investigating the collective electron behavior in confined systems. However, clear identification of atomic structures at the grain boundaries, as well as precise characterization of the electronic ground states, have largely been elusive. Here, direct evidence for the confined electronic states and the charge density modulations at mirror twin boundaries (MTBs) of monolayer NbSe2 , a representative charge-density-wave (CDW) metal, is provided. The scanning tunneling microscopy (STM) measurements, accompanied by the first-principles calculations, reveal that there are two types of MTBs in monolayer NbSe2 , both of which exhibit band bending effect and 1D boundary states. Moreover, the intrinsic CDW signatures of monolayer NbSe2 are dramatically suppressed as approaching an isolated MTB but can be either enhanced or suppressed in the MTB-constituted confined wedges. Such a phenomenon can be well explained by the MTB-CDW interference interactions. The results reveal the underlying physics of the confined electrons at MTBs of CDW metals, paving the way for the grain boundary engineering of the functionality.

Visualizing Spatial Evolution of Electron-Correlated Interface in Two-Dimensional Heterostructures.

Microscopically visualizing the evolution of electronic structures at the interface between two electron-correlated domains shows fundamental importance in both material science and physics. Here, we report scanning tunneling microscopy and spectroscopy studies of the interfacial electronic structures evolution in a phase-engineered monolayer NbSe2 heterostructure. The H-NbSe2 metallic state penetrates the Mott insulating T-NbSe2 at the H/T phase interface, with a prominent 2D charge density wave (CDW) proximity effect. Moreover, an insulating Mott gap collapse with the disappearance of the upper Hubbard band is detected at the electronic phase transition region. Theoretical calculations reveal that such insulating Mott gap collapse can be attributed to the electron doping effect induced by the interface. Our findings promote a microscopical understanding of the interactions between different electron-correlated systems and provide an effective method for controlling the Mott insulating states with phase engineering.