Vapor Deposition of Bilayer 3R MoS2 with Room-Temperature Ferroelectricity.

Two-dimensional ultrathin ferroelectrics have attracted much interest due to their potential application in high-density integration of non-volatile memory devices. Recently, 2D van der Waals ferroelectric based on interlayer translation has been reported in twisted bilayer h-BN and transition metal dichalcogenides (TMDs). However, sliding ferroelectricity is not well studied in non-twisted homo-bilayer TMD grown directly by chemical vapor deposition (CVD). In this paper, for the first time, experimental observation of a room-temperature out-of-plane ferroelectric switch in semiconducting bilayer 3R MoS2 synthesized by reverse-flow CVD is reported. Piezoelectric force microscopy (PFM) hysteretic loops and first principle calculations demonstrate that the ferroelectric nature and polarization switching processes are based on interlayer sliding. The vertical Au/3R MoS2/Pt device exhibits a switchable diode effect. Polarization modulated Schottky barrier height and polarization coupling of interfacial deep states trapping/detrapping may serve in coordination to determine switchable diode effect. The room-temperature ferroelectricity of CVD-grown MoS2 will proceed with the potential wafer-scale integration of 2D TMDs in the logic circuit.

Superior piezoelectric performance of chemically synthesized transition metal dichalcogenide heterostructures for self-powered flexible piezoelectric nanogenerator.

In addition to the superior electrical and optoelectronic attributes, ultrathin two-dimensional transition metal dichalcogenides (TMDCs) have evoked appreciable attention for their piezoelectric properties. In this study, we report, the piezoelectric characteristics of large area, chemically exfoliated TMDCs and their heterostructures for the first time, as verified by piezoelectric force microscopy measurements. Piezoelectric output voltage response of the MoS2-WSe2heterostructure piezoelectric nanogenerator (PENG) is enhanced by ∼47.5% if compared with WSe2and ∼29% if compared to MoS2PENG, attributed to large band offset induced by heterojunction formation. This allows the scalable fabrication of self-powered energy harvesting PENGs, which can overcome the various shortcomings of complicated synthesis processes, complex fabrication steps, low yield, and poor stability. The fabricated flexible, self-powered MoS2-WSe2heterostructure nanogenerator exhibits piezoelectric output ∼46 mV under a strain of ∼0.66% yielding a power output ∼12.3 nW, which offers better performance than other two-dimensional material based piezoelectric devices and also reveals the ability of bio-mechanical energy harvesting. This cost effective approach to fabricate eco-friendly MoS2-WSe2based fatigue free, superior performance piezoelectric-nanogenerators can be utilized to evolve flexible energy harvesting devices and may also be attractive as a self-powered, smart wearable sensor devices.

Piezoelectric Responses of Mechanically Exfoliated Two-Dimensional SnS2 Nanosheets.

The emergence of piezoelectric properties in two-dimensional (2D) layered transition metal dichalcogenides (TMDs) has triggered the intensive research on using low dimensional materials for conversion of mechanical stimuli into electrical signals or vice versa. While the bulk intrinsically presents no piezoelectric property, the origin of the piezoelectric responses in their 2D thin planes is ascribed to the loss of centrosymmetry. There are also other categories of 2D layered materials such as post-transition metal dichalcogenides (PTMDs) that might be of interests, which have been confirmed theoretically and are yet to be fully explored experimentally. In this work, we investigate the thickness-dependent piezoelectric responses of 2D tin disulfide (SnS2) nanosheets as a representative of layered PTMDs. The results indicate that the 2D SnS2 nanosheets with a thickness of ∼4 nm present an effective out-of-plane piezoelectric response of 2 ± 0.22 pm/V. Furthermore, the thickness dependence of the piezoelectric behavior at a resonant frequency shows that the piezoelectric coefficient decreases with increasing the thickness of 2D SnS2 nanosheets. Additionally, in reference to periodically poled lithium niobate piezoelectric crystal, the measured effective lateral piezoelectric coefficients at different voltages range from 0.61 to 1.55 pm/V with the average value at ∼1 pm/V. This study expands candidates for new piezoelectric materials in the 2D domain with comparable vertical and lateral coefficients, potentially opening a broader horizon for integration into sensors, actuators, and micro- and nanoelectromechanical systems.

Self-Organized Formation of Quasi-Regular Ferroelectric Nanodomain Structure on the Nonpolar Cuts by Grounded SPM Tip.

The understanding of self-organization processes at the micro- and nanoscale is of fundamental interest and is important to meet the great challenges in further miniaturization of electronic devices to the nanoscale. Here, we report self-organized quasi-regular nanodomain structure formation on the nonpolar cut of a ferroelectric lithium niobate single crystal. These structures were formed along the trajectory of grounded scanning probe microscope tip approaching or moving away from the freshly switched region. Detailed analysis of the formed structures revealed internal organization by the length of the needle-like domains, which ranged from uniform to quasi-periodic and even chaotic modes as a function of distance from the switched region. Comprehensive investigations and numerical simulations allowed to attribute explored phenomena to charge injection during the field application and further switching under the action of electric field induced by injected charges near the tip. Self-organization and quasi-periodicity were explained by the effective screening and long-range electrostatic interaction between the individual needle-like domains.

The Narrowest Band Gap Ever Observed in Molecular Ferroelectrics: Hexane-1,6-diammonium Pentaiodobismuth(III).

Narrow band gaps and excellent ferroelectricity are intrinsically paradoxical in ferroelectrics as the leakage current caused by an increase in the number of thermally excited carriers will lead to a deterioration of ferroelectricity. A new molecular ferroelectric, hexane-1,6-diammonium pentaiodobismuth (HDA-BiI5 ), was now developed through band gap engineering of organic-inorganic hybrid materials. It features an intrinsic band gap of 1.89 eV, and thus represents the first molecular ferroelectric with a band gap of less than 2.0 eV. Simultaneously, low-temperature solution processing was successfully applied to fabricate high-quality ferroelectric thin films based on HDA-BiI5 , for which high-precision controllable domain flips were realized. Owing to its narrow band gap and excellent ferroelectricity, HDA-BiI5 can be considered as a milestone in the exploitation of molecular ferroelectrics, with promising applications in high-density data storage and photovoltaic conversion.

The Formation of Self-Organized Domain Structures at Non-Polar Cuts of Lithium Niobate as a Result of Local Switching by an SPM Tip.

We have studied experimentally the interaction of isolated needle-like domains created in an array via local switching using a biased scanning probe microscope (SPM) tip and visualized via piezoelectric force microscopy (PFM) at the non-polar cuts of MgO-doped lithium niobate (MgOLN) crystals. It has been found that the domain interaction leads to the intermittent quasiperiodic and chaotic behavior of the domain length in the array in a manner similar to that of polar cuts, but with greater spacing between the points of bias application and voltage amplitudes. It has also been found that the polarization reversal at the non-polar cuts and domain interaction significantly depend on humidity. The spatial distribution of the surface potential measured by Kelvin probe force microscopy in the vicinity of the charged domain walls revealed the decrease of the domain length as a result of the partial backswitching after pulse termination. The phase diagram of switching behavior as a function of tip voltage and spacing between the points of bias application has been plotted. The obtained results provide new insight into the problem of the domain interaction during forward growth and can provide a basis for useful application in nanodomain engineering and development of non-linear optical frequency converters, data storage, and computing devices.

Polarization Switching and Light-Enhanced Piezoelectricity in Lead Halide Perovskites.

We investigate the ferroelectric properties of photovoltaic methylammonium lead halide CH3NH3PbI3 perovskite using piezoelectric force microscopy (PFM) and macroscopic polarization methods. The electric polarization is clearly observed by amplitude and phase hysteresis loops. However, the polarization loop decreases as the frequency is lowered, persisting for a short time only, in the one second regime, indicating that CH3NH3PbI3 does not exhibit permanent polarization at room temperature. This result is confirmed by macroscopic polarization measurement based on a standard capacitive method. We have observed a strong increase of piezoelectric response under illumination, consistent with the previously reported giant photoinduced dielectric constant at low frequencies. We speculate that an intrinsic charge transfer photoinduced dipole in the perovskite cage may lie at the origin of this effect.

A molecular ferroelectric thin film of imidazolium perchlorate that shows superior electromechanical coupling.

Molecular ferroelectric thin films are highly desirable for their easy and environmentally friendly processing, light weight, and mechanical flexibility. A thin film of imidazolium perchlorate processed from aqueous solution is an excellent molecular ferroelectric with high spontaneous polarization, high Curie temperature, low coercivity, and superior electromechanical coupling. These attributes make it a molecular alternative to perovskite ferroelectric films in sensing, actuation, data storage, electro-optics, and molecular/flexible electronics.