Control over a Wide Phase Diagram of 2D Correlated Electrons by Surface Doping; K/1T-TaS2.

We demonstrate the systematic tuning of a trivial insulator into a Mott insulator and a Mott insulator into a correlated metallic and a pseudogap state, which emerge in a quasi-two-dimensional electronic system of 1T-TaS2 through strong electron correlation. The band structure evolution is investigated upon surface doping by alkali adsorbates for two distinct phases occurring at around 220 and 10 K by angle-resolved photoelectron spectroscopy. We find contrasting behaviors upon doping that corroborate the fundamental difference of two electronic states: while the antibonding state of the spin-singlet insulator at 10 K is partially occupied to produce an emerging Mott insulating state, the presumed Mott insulating state at 220 K evolves into a correlated metallic state and then a pseudogap state. The work indicates that surface doping onto correlated 2D materials can be a powerful tool to systematically engineer a wide range of correlated electronic phases.

Raman Optical Activity of 1T-TaS2.

Measurements of optical activity can be readily performed in transparent matter by means of a rotation of transmitted light polarization. In the case of opaque bulk materials, such measurements cannot be performed, making it difficult to assess possible chiral properties. In this work, we present full angular polarization dependencies of the Raman modes of bulk 1T-TaS2, which has recently been suggested to have chiral properties after pulsed laser excitation. We found that a mechanical rotation of the sample does not alter polarization-resolved Raman spectra, which can only be explained by introducing an antisymmetric Raman tensor, frequently used to describe Raman optical activity (ROA). Raman spectra obtained under circularly polarized excitation demonstrate that 1T-TaS2 indeed shows ROA, providing strong evidence that 1T-TaS2 is chiral under the used conditions of laser excitation. Our results suggest that ROA may be used as a universal tool to study chiral properties of quantum materials.

Charge Density Wave Vortex Lattice Observed in Graphene-Passivated 1T-TaS2 by Ambient Scanning Tunneling Microscopy.

The nearly commensurate charge density wave (CDW) excitations native to the transition-metal dichalcogenide crystal, 1T-TaS2, under ambient conditions are revealed by scanning tunneling microscopy (STM) and spectroscopy (STS) measurements of a graphene/TaS2 heterostructure. Surface potential measurements show that the graphene passivation layer prevents oxidation of the air-sensitive 1T-TaS2 surface. The graphene protective layer does not however interfere with probing the native electronic properties of 1T-TaS2 by STM/STS, which revealed that nearly commensurate CDW hosts an array of vortex-like topological defects. We find that these topological defects organize themselves to form a lattice with quasi-long-range order, analogous to the vortex Bragg glass in type-II superconductors but accessible in ambient conditions.

A Tantalum Disulfide Charge-Density-Wave Stochastic Artificial Neuron for Emulating Neural Statistical Properties.

Artificial neuronal devices that functionally resemble biological neurons are important toward realizing advanced brain emulation and for building bioinspired electronic systems. In this Communication, the stochastic behaviors of a neuronal oscillator based on the charge-density-wave (CDW) phase transition of a 1T-TaS2 thin film are reported, and the capability of this neuronal oscillator to generate spike trains with statistical features closely matching those of biological neurons is demonstrated. The stochastic behaviors of the neuronal device result from the melt-quench-induced reconfiguration of CDW domains during each oscillation cycle. Owing to the stochasticity, numerous key features of the Hodgkin-Huxley description of neurons can be realized in this compact two-terminal neuronal oscillator. A statistical analysis of the spike train generated by the artificial neuron indicates that it resembles the neurons in the superior olivary complex of a mammalian nervous system, in terms of its interspike interval distribution, the time-correlation of spiking behavior, and its response to acoustic stimuli.

Phase Transition Photodetection in Charge Density Wave Tantalum Disulfide.

The charge density wave (CDW) phase is a macroscopic quantum state with periodic charge density modulation accompanied by periodic lattice distortion in low-dimensional metals. External fields, such as an electric field and optical excitation, can trigger the transitions among different CDW states, leaving an under-explored mechanism and attracting great interest toward optoelectronic applications. Here, we explore a photoinduced phase transition in 1T-TaS2 under an electrical field. By analyzing the phase transition probability, we obtained a linear dependence of the phase transition barrier on the electric field and laser energy density. Additionally, the threshold laser energy for the phase transition decreases linearly with an increasing applied electrical field. Finally, picojoule photodetection was realized in the visible and near-infrared ranges near the CDW transition edge. Our work will promote the understanding of the CDW phase transition mechanism as well as open pathways for optoelectronic applications.

Single-water-dipole-layer-driven Reversible Charge Order Transition in 1T-TaS2.

Water-solid interactions are crucial for many fundamental phenomena and technological processes. Here, we report a scanning tunneling microscopy study about the charge density wave (CDW) transition in 1T-TaS2 driven by a single water dipole layer. At low temperature, pristine 1T-TaS2 is a prototypical CDW compound with 13 × 13 charge order. After growing a highly ordered water adlayer, a new charge order with 3 × 3 periodicity emerges on water-covered 1T-TaS2. After water desorption, the entire 1T-TaS2 surface appears as localized 13 × 13 CDW domains that are separated by residual-water-cluster-pinned CDW domain walls. First-principles calculations show that the electric dipole moments in the water adlayer attract electrons to the top layer of 1T-TaS2, which shifts the phonon softening mode and induces the 13 × 13 to 3 × 3 charge order transition. Our results pave the way for creating new collective quantum states of matter with a molecular dipole layer.

Large Optical Tunability from Charge Density Waves in 1T-TaS2 under Incoherent Illumination.

Strongly correlated materials possess a complex energy landscape and host many interesting physical phenomena, including charge density waves (CDWs). CDWs have been observed and extensively studied in many materials since their first discovery in 1972. Yet they present ample opportunities for discovery. Here, we report a large tunability in the optical response of a quasi-2D CDW material, 1T-TaS2, upon incoherent light illumination at room temperature. We hypothesize that the observed tunability is a consequence of light-induced rearrangement of CDW stacking across the layers of 1T-TaS2. Our model, based on this hypothesis, agrees reasonably well with experiments suggesting that the interdomain CDW interaction is a vital potentially knob to control the phase of strongly correlated materials.

Raman Spectroscopic and Dynamic Electrical Investigation of Multi-State Charge-Wave-Density Phase Transitions in 1 T-TaS2.

Two-dimensional layered 1 T-TaS2 exhibits rich charge-density-wave (CDW) states with distinct electronic structures and physical properties, leading to broad potential applications, such as phase-transition memories, electrical oscillators and photodetectors. Besides the various CDW ground states at different temperatures, multiple intermediate phases in 1 T-TaS2 have been observed by applying optical and electrical stimulations. Here, we investigated the electric-field-driven multistate CDW phase transition by Raman spectroscopy and voltage oscillations in 1 T-TaS2. Strong correlation was observed between electrical conductivity and intensity of fold-back acoustic and optical phonon modes in 1 T-TaS2. This indicates that the multistate transitions arise from serial transitions, from the nearly commensurate (NC) CDW phase to out-of-equilibrium intermediate states, and finally to the incommensurate (IC) CDW phase. The dynamics of phase transition under an electric field was investigated. As the electrical field increased, the dwell time of different CDW states changed. At lower temperatures, the multistate oscillations disappeared because of higher-energy barriers between the intermediate phases and/or lower thermal excitation energies at lower temperatures.

Modulating Charge Density Wave Order in a 1T-TaS2/Black Phosphorus Heterostructure.

Controllability of collective electron states has been a long-sought scientific and technological goal and promises development of new devices. Herein, we investigate the tuning of charge density wave (CDW) in 1T-TaS2 via a two-dimensional (2D) van der Waals heterostructure of 1T-TaS2/BP. Unusual gate-dependent conductance oscillations were observed in 1T-TaS2 nanoflake supported on BP in transport measurements. Scanning tunneling microscopy study shows that the nearly commensurate (NC) CDW phase survived to 4.5 K in this system, which is substantially lower than the NC to commensurate CDW phase transition temperature of 180 K. A Coulomb blockade model was invoked to explain the conductance oscillations, where the domain walls and domains in NC phase serve as series of quantum dot arrays and tunnelling barriers, respectively. Density functional theory calculations show that a range of interfacial interactions, including strain and charge transfer, influences the CDW stabilities. Our work sheds light on tuning CDW orders via 2D heterostructure stacking and provides new insights on the CDW phase transition and sliding mechanism.

Low-Frequency Current Fluctuations and Sliding of the Charge Density Waves in Two-Dimensional Materials.

We investigated low-frequency noise in two-dimensional (2D) charge density wave (CDW) systems, 1 T-TaS2 thin films, as they were driven from the nearly commensurate (NC) to incommensurate (IC) CDW phases by voltage and temperature stimuli. This study revealed that noise in 1 T-TaS2 has two pronounced maxima at the bias voltages, which correspond to the onset of CDW sliding and the NC-to-IC phase transition. We observed unusual Lorentzian features and exceptionally strong noise dependence on electric bias and temperature, leading to the conclusion that electronic noise in 2D CDW systems has a unique physical origin different from known fundamental noise types. We argue that noise spectroscopy can serve as a useful tool for understanding electronic transport phenomena in 2D CDW materials characterized by coexistence of different phases and strong pinning.

Tuning Phase Transitions in 1T-TaS2 via the Substrate.

Phase transitions in 2D materials can lead to massive changes in electronic properties that enable novel electronic devices. Tantalum disulfide (TaS2), specifically the "1T" phase (1T-TaS2), exhibits a phase transition based on the formation of commensurate charge density waves (CCDW) at 180 K. In this work, we investigate the impact of substrate choice on the phase transitions in ultrathin 1T-TaS2. Doping and charge transfer from the substrate has little impact on CDW phase transitions. On the contrary, we demonstrated that substrate surface roughness is a primary extrinsic factor in CCDW transition temperature and hysteresis, where higher roughness leads to smaller transition hysteresis. Such roughness can be simulated via surface texturing of SiO2/Si substrates, which controllably and reproducibly induces periodic strain in the 1T-TaS2 and thereby enables the potential for engineering CDW phase transitions.

Electrically driven reversible insulator-metal phase transition in 1T-TaS2.

In this work, we demonstrate abrupt, reversible switching of resistance in 1T-TaS2 using dc and pulsed sources, corresponding to an insulator-metal transition between the insulating Mott and equilibrium metallic states. This transition occurs at a constant critical resistivity of 7 mohm-cm regardless of temperature or bias conditions and the transition time is significantly smaller than abrupt transitions by avalanche breakdown in other small gap Mott insulating materials. Furthermore, this critical resistivity corresponds to a carrier density of 4.5 × 10(19) cm(-3), which compares well with the critical carrier density for the commensurate to nearly commensurate charge density wave transition. These results suggest that the transition is facilitated by a carrier driven collapse of the Mott gap in 1T-TaS2, which results in fast (3 ns) switching.

Kinkless Electronic Junction along 1D Electronic Channel Embedded in a Van Der Waals Layer.

Here, the formation of type-I and type-II electronic junctions with or without any structural discontinuity along a well-defined 1 nm-wide 1D electronic channel within a van der Waals layer is reported. Scanning tunneling microscopy and spectroscopy techniques are employed to investigate the atomic and electronic structure along peculiar domain walls formed on the charge-density-wave phase of 1T-TaS2 . Distinct kinds of abrupt electronic junctions with discontinuities of the band gap along the domain walls are found, some of which even do not have any structural kinks and defects. Density-functional calculations reveal a novel mechanism of the electronic junction formation; they are formed by a kinked domain wall in the layer underneath through substantial electronic interlayer coupling. This work demonstrates that the interlayer electronic coupling can be an effective control knob over nanometer-scale electronic property of 2D atomic monolayers.

Selective Electron-Phonon Coupling in Dimerized 1T-TaS2 Revealed by Resonance Raman Spectroscopy.

The layered transition-metal dichalcogenide material 1T-TaS2 possesses successive phase transitions upon cooling, resulting in strong electron-electron correlation effects and the formation of charge density waves (CDWs). Recently, a dimerized double-layer stacking configuration was shown to form a Peierls-like instability in the electronic structure. To date, no direct evidence for this double-layer stacking configuration using optical techniques has been reported, in particular through Raman spectroscopy. Here, we employ a multiple excitation and polarized Raman spectroscopy to resolve the behavior of phonons and electron-phonon interactions in the commensurate CDW lattice phase of dimerized 1T-TaS2. We observe a distinct behavior from what is predicted for a single layer and probe a richer number of phonon modes that are compatible with the formation of double-layer units (layer dimerization). The multiple-excitation results show a selective coupling of each Raman-active phonon with specific electronic transitions hidden in the optical spectra of 1T-TaS2, suggesting that selectivity in the electron-phonon coupling must also play a role in the CDW order of 1T-TaS2.

Nanoscale Friction across the First-Order Charge Density Wave Phase Transition of 1T-TaS2.

Nanotribology using atomic force microscopy (AFM) can be considered as a unique approach to analyze phase transition materials by localized mechanical interaction. In this work, we investigate friction on the lamellar transition metal dichalcogenide 1T-TaS2, which can undergo first-order charge density wave (CDW) phase transitions. Based on temperature-dependent atomic force microscopy under ultrahigh vacuum conditions (UHV), we can characterize the general friction levels across the first-order phase transitions and for the different phases. While structural and electronic properties for different phases appear to be of minor influence on friction, a distinct peak in friction is observed during the phase transition when cooling the sample from the nearly commensurate CDW (NC-CDW) phase to the commensurate CDW (C-CDW) phase. By performing systematic measurements as a function of load, scan velocity, and scan time, a recently proposed friction mechanism can be corroborated, where the AFM tip gradually induces local transformations of the material close to the spinodal point in a thermally activated and shear-assisted process until the surface is fully "harvested". Our results demonstrate that repeated nanomechanical stress can trigger local first-order phase transitions constituting a so far little explored mechanical energy dissipation channel.

Controllable Synthesis and Charge Density Wave Phase Transitions of Two-Dimensional 1T-TaS2 Crystals.

1T-TaS2 has attracted much attention recently due to its abundant charge density wave phases. In this work, high-quality two-dimensional 1T-TaS2 crystals were successfully synthesized by a chemical vapor deposition method with controllable layer numbers, confirmed by the structural characterization. Based on the as-grown samples, their thickness-dependency nearly commensurate charge density wave/commensurate charge density wave phase transitions was revealed by the combination of the temperature-dependent resistance measurements and Raman spectra. The phase transition temperature increased with increasing thickness, but no apparent phase transition was found on the 2~3 nm thick crystals from temperature-dependent Raman spectra. The transition hysteresis loops due to temperature-dependent resistance changes of 1T-TaS2 can be used for memory devices and oscillators, making 1T-TaS2 a promising material for various electronic applications.

Controlling magnetic frustration in 1T-TaS2via Coulomb engineered long-range interactions.

Magnetic frustrations in two-dimensional materials provide a rich playground to engineer unconventional phenomena. However, despite intense efforts, a realization of tunable frustrated magnetic order in two-dimensional materials remains an open challenge. Here we propose Coulomb engineering as a versatile strategy to tailor magnetic ground states in layered materials. Using the frustrated van der Waals monolayer 1T-TaS2as an example, we show how long-range Coulomb interactions renormalize the low energy nearly flat band structure, leading to a Heisenberg model which depends on the Coulomb interactions. Based on this, we show that superexchange couplings in the material can be precisely tailored by means of environmental dielectric screening, ultimately allowing to externally drive the material towards a tunable frustrated regime. Our results put forward Coulomb engineering as a powerful tool to manipulate magnetic properties of van der Waals materials.

Charge-Density-Wave Thin-Film Devices Printed with Chemically Exfoliated 1T-TaS2 Ink.

We report on the preparation of inks containing fillers derived from quasi-two-dimensional charge-density-wave materials, their application for inkjet printing, and the evaluation of their electronic properties in printed thin-film form. The inks were prepared by liquid-phase exfoliation of CVT-grown 1T-TaS2 crystals to produce fillers with nm-scale thickness and µm-scale lateral dimensions. Exfoliated 1T-TaS2 was dispersed in a mixture of isopropyl alcohol and ethylene glycol to allow fine-tuning of filler particles thermophysical properties for inkjet printing. The temperature-dependent electrical and current fluctuation measurements of printed thin films demonstrated that the charge-density-wave properties of 1T-TaS2 are preserved after processing. The functionality of the printed thin-film devices can be defined by the nearly commensurate to the commensurate charge-density-wave phase transition of individual exfoliated 1T-TaS2 filler particles rather than by electron-hopping transport between them. The obtained results are important for the development of printed electronics with diverse functionality achieved by the incorporation of quasi-two-dimensional van der Waals quantum materials.

Gate- and Light-Tunable Negative Differential Resistance with High Peak Current Density in 1T-TaS2/2H-MoS2 T-Junction.

Metal-based electronics is attractive for fast and radiation-hard electronic circuits and remains one of the long-standing goals for researchers. The emergence of 1T-TaS2, a layered material exhibiting strong charge density wave (CDW)-driven resistivity switching that can be controlled by an external stimulus such as electric field and optical pulses, has triggered a renewed interest in metal-based electronics. Here we demonstrate a negative differential resistor (NDR) using electrically driven CDW phase transition in an asymmetrically designed T-junction made up of 1T-TaS2/2H-MoS2 van der Waals heterojunction. The principle of operation of the proposed device is governed by majority carrier transport and is distinct from usual NDR devices employing tunneling of carriers; thus it avoids the bottleneck of weak tunneling efficiency in van der Waals heterojunctions. Consequently, we achieve a peak current density in excess of 105 nA µm-2, which is about 2 orders of magnitude higher than that obtained in typical layered material based NDR implementations. The peak current density can be effectively tuned by an external gate voltage as well as photogating. The device is robust against ambiance-induced degradation, and the characteristics repeat in multiple measurements over a period of more than a month. The findings are attractive for the implementation of active metal-based functional circuits.

Light-Tunable 1T-TaS2 Charge-Density-Wave Oscillators.

External stimuli-controlled phase transitions are essential for fundamental physics and design of functional devices. Charge density wave (CDW) is a metastable collective electronic phase featured by the periodic lattice distortion. Much attention has been attracted to study the external control of CDW phases. Although much work has been done in the electric-field-induced CDW transition, the study of the role of Joule heating in the phase transition is insufficient. Here, using the Raman spectroscopy, the electric-field-driven phase transition is in situ observed in the ultrathin 1T-TaS2. By quantitative evaluation of the Joule heating effect in the electric-field-induced CDW transition, it is shown that Joule heating plays a secondary role in the nearly commensurate (NC) to incommensurate (IC) CDW transition, while it dominants the IC-NC CDW transition, providing a better understanding of the electric field-induced phase transition. More importantly, at room temperature, light illumination can modulate the CDW phase and thus tune the frequency of the ultrathin 1T-TaS2 oscillators. This light tunability of the CDW phase transition is promising for multifunctional device applications.