RESUMEN

Lithium-rich layered oxides (LLOs) capable of supporting both cationic and anionic redox chemistry are promising cathode materials. Yet, their initial charge to high voltages often trigger significant oxygen evolution, resulting in substantial capacity loss and structural instability. In this study, we applied a straightforward low-potential activation (LOWPA) method alongside a relatively stable electrolyte to address this issue. This approach enables precise control over the order-to-disorder transformation of the transition metal layers in LLOs, producing an in-plane cation-disordered Li1.2Mn0.54Co0.13Ni0.13O2 that averts irreversible oxygen evolution at 4.8 V by stabilizing Mn-O2 or Mn-O3 species within the Li/Mn-disordered nanopores. Consequently, an ultrahigh reversible capacity of 322 mAh g-1 (equating to 1141 Wh kg-1), 91.5% initial Coulombic efficiency, and enhanced durability and rate capability are simultaneously achieved. As LOWPA does not alter any chemical composition of LLOs, it also offers a simple model for untangling the complex phenomena associated with oxygen-redox chemistry.

RESUMEN

Two-dimensional (2D) ferroelectric semiconductors present opportunities for integrating ferroelectrics into high-density ultrathin nanoelectronics. Among the few synthesized 2D ferroelectrics, α-In2Se3, known for its electrically addressable vertical polarization, has attracted significant interest. However, the understanding of many fundamental characteristics of this material, such as the existence of spontaneous in-plane polarization and switching mechanisms, remains controversial, marked by conflicting experimental and theoretical results. Here, our combined experimental characterizations with piezoresponse force microscope and symmetry analysis conclusively dismiss previous claims of in-plane ferroelectricity in single-domain α-In2Se3. The processes of vertical polarization switching in monolayer α-In2Se3 are explored with deep-learning-assisted large-scale molecular dynamics simulations, revealing atomistic mechanisms fundamentally different from those of bulk ferroelectrics. Despite lacking in-plane effective polarization, 1D domain walls can be moved by both out-of-plane and in-plane fields, exhibiting avalanche dynamics characterized by abrupt, intermittent moving patterns. The propagating velocity at various temperatures, field orientations, and strengths can be statistically described with a universal creep equation, featuring a dynamical exponent of 2 that is distinct from all known values for elastic interfaces moving in disordered media. This work rectifies a long-held misunderstanding regarding the in-plane ferroelectricity of α-In2Se3, and the quantitative characterizations of domain wall velocity will hold broad implications for both the fundamental understanding and technological applications of 2D ferroelectrics.

RESUMEN

Two-dimensional (2D) molybdenum disulfide (MoS2), one of the most extensively studied van der Waals (vdW) materials, is a significant candidate for electronic materials in the post-Moore era. MoS2 exhibits various phases, among which the 1T‴ phase possesses noncentrosymmetry. 1T‴-MoS2 was theoretically predicted to be ferroelectric a decade ago, but this has not been experimentally confirmed until now. Here, we have prepared high-purity 2D 1T‴-MoS2 crystals and experimentally confirmed the room-temperature out-of-plane ferroelectricity. The noncentrosymmetric crystal structure in 2D 1T‴-MoS2 was convinced by atomically resolved transmission electron microscopic imaging and second harmonic generation (SHG) measurements. Further, the ferroelectric polarization states in 2D 1T‴-MoS2 can be switched using piezoresponse force microscopy (PFM) and electrical gating in field-effect transistors (FETs). The ferroelectric-to-paraelectric transition temperature is measured to be about 350 K. Theoretical calculations have revealed that the ferroelectricity of 2D 1T‴-MoS2 originates from the intralayer charge transfer of S atoms within the layer. The discovery of intrinsic ferroelectricity in the 1T‴ phase of MoS2 further enriches the properties of this important vdW material, providing more possibilities for its application in the field of next-generation electronic devices.

RESUMEN

Two-dimensional (2D) ferroelectrics promise ultrathin flexible nanoelectronics, typically utilizing a metal-ferroelectric-metal sandwich structure. Electrodes can either contribute free carriers to screen the depolarization field, enhancing nanoscale ferroelectricity, or induce charge doping, disrupting the long-range crystalline order. We explore electrodes' dual roles in 2D ferroelectric capacitors, supported by first-principles calculations covering a range of electrode work functions. Our results reveal volcano-type relationships between ferroelectric-electrode binding affinity and work function, which are further unified by a quadratic scaling between the binding energy and the transferred interfacial charge. At the monolayer limit, charge transfer dictates the ferroelectric stability and switching properties. This general characteristic is confirmed in various 2D ferroelectrics including α-In2Se3, CuInP2S6, and SnTe. As the ferroelectric layer's thickness increases, the capacitor stability evolves from a charge-transfer-dominated state to a screening-dominated state. The delicate interplay between these two effects has important implications for 2D ferroelectric capacitor applications.

RESUMEN

Long-range ferroelectric crystalline order usually fades away as the spatial dimension decreases, and hence there are few two-dimensional (2D) ferroelectrics and far fewer one-dimensional (1D) ferroelectrics. Due to the depolarization field, low-dimensional ferroelectrics rarely possess the polarization along the direction of reduced dimensionality. Here, using first-principles density functional theory, we explore the structural evolution of nanoribbons of varying widths constructed by cutting a 2D sheet of ferroelectric α-III2VI3 (III = Al, Ga, In; VI = S, Se, Te). We discover a one-dimensional ferroelectric nanothread (1DFENT) of ultrasmall diameter with both axial and radial polarization, potentially enabling ultra-dense data storage with a 1D domain of just three unit cells being the functional unit. The polarization in 1DFENT of Ga2Se3 exhibits an unusual piezoelectric response: a stretching stress along the axial direction will increase both the axial and radial polarization, referred to as the auxetic piezoelectric effect. Utilizing the intrinsically flat electronic bands, we demonstrate the coexistence of ferroelectricity and ferromagnetism in 1DFENT and a counterintuitive charge-doping-induced metal-to-insulator transition. The 1DFENT with both axial and radial polarization offers a counterexample to the Mermin-Wagner theorem in 1D and suggests a new platform for the design of ultrahigh-density memory and the exploration of exotic states of matter.

RESUMEN

The integration of ferroelectrics that exhibit high dielectric, piezoelectric, and thermal compatibility with the mainstream semiconductor industry will enable novel device types for widespread applications, and yet there are few silicon-compatible ferroelectrics suitable for device downscaling. We demonstrate with first-principles calculations that the enhanced depolarization field at the nanoscale can be utilized to soften unswitchable wurtzite III-V semiconductors, resulting in ultrathin two-dimensional (2D) sheets possessing reversible polarization states. A 2D sheet of AlSb consisting of three atomic planes is identified to host both ferroelectricity and antiferroelectricity, and the tristate switching is accompanied by a metal-semiconductor transition. The thermodynamic stability and potential synthesizability of the triatomic layer are corroborated with phonon spectrum calculations, ab initio molecular dynamics simulations, and variable-composition evolutionary structure search. We propose a 2D AlSb-based homojunction field effect transistor that supports three distinct and nonvolatile resistance states. This new class of III-V semiconductor-derived 2D materials with dual ferroelectricity and antiferroelectricity opens up the opportunity for nonvolatile multibit-based integrated nanoelectronics.

RESUMEN

Raman spectra are often masked by strong fluorescence, which severely hinders the applications of Raman spectroscopy. Herein, for the first time, we report ionic-wind-enhanced Raman spectroscopy (IWERS) incorporated with photobleaching (PB) as a noninvasive approach to detect fluorescent and vulnerable samples without a substrate. In this study, ionic wind (IW) generated by needle-net electrodes transfers charges to the sample surface in air on the scale of millimeters rather than nanometers in surface-enhanced Raman spectroscopy. Density functional theory calculations reveal that the ionic particles in IW increase the susceptibility of the sample molecules, thus enhancing the Raman signals. Meanwhile, the incorporation of IW with PB yields a synergistic effect to quench fluorescence. Therefore, this approach can improve the signal-to-noise ratio of Raman peaks up to three times higher than that with only PB. At the same time, IWERS can avoid sample pollution and destruction without substrates as well as high laser power. For archeological samples and a red rock as an analogue to Mars geological samples, IWERS successfully identified weak but key Raman peaks, which were masked by strong florescence. It suggests that IWERS is a promising tool for characterizations in the fields of archeology, planetary science, biomedicine, and soft matter.

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RESUMEN

The coexistence of metallicity and ferroelectricity has been an intriguing and controversial phenomenon as these two material properties are considered incompatible in bulk. We clarify the concept of the ferroelectric metal by revisiting the original definitions for ferroelectric and metal. Two-dimensional (2D) ferroelectrics with out-of-plane polarization can be engineered via layer stacking to a genuine ferroelectric metal characterized by switchable polarization and non-zero density of states at the Fermi level. We demonstrate that 2D ferroelectric metals can serve as electrically-tunable, high-quality electrocatalysts.

RESUMEN

Dehydrogenation of H3COH and H2O are key steps of methanol steam reforming on transition metal surfaces. Oxhydryl dehydrogenation reactions of HxCOH (x = 0-3) and OH on Ni (111) were investigated by DFT calculations with the OptB88-vdW functional. The transition states were searched by the climbing image nudged elastic band method and the dimer method. The activation energies for the dehydrogenation of individual HxCOH* are 68 to 91 kJ/mol, and reduced to 12-17 kJ/mol by neighboring OH*. Bader charge analysis showed the catalysis role of OH* can be attributed to the effect of hydrogen bond (H-bond) in maintaining the charge of oxhydryl H in the reaction path. The mechanism of H-bond catalysis was further demonstrated by the study of OH* and N* assisted dehydrogenation of OH*. Due to the universality of H-bond, the H-bond catalysis shown here, is of broad implication for studies of reaction kinetics.

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