Ferroelectric Hysteresis in Singly Aligned Graphene-hBN Moiré Superlattices.

Dislocations corresponding to a change of stacking in two-dimensional hexagonal bilayers, graphene and boron nitride, and associated with boundaries between commensurate domains are investigated using the two-chain Frenkel-Kontorova model on top of ab initio calculations. Structural transformations of bilayers in which the bottom layer is stretched and the upper one is left to relax freely are considered for gradually increased elongation of the bottom layer. Formation energies of dislocations, dislocation width and orientation of the boundary between commensurate domains are analyzed depending on the magnitude and direction of elongation. The second-order phase transition from the commensurate phase to the incommensurate one with multiple dislocations is predicted to take place at some critical elongation. The order parameter for this transition corresponds to the density of dislocations, which grows continuously upon increasing the elongation of the bottom layer above the critical value. In graphene and metastable boron nitride with the layers aligned in the same direction, where elementary dislocations are partial, this transition, however, is preceded by formation of the first dislocation at the elongation smaller than the critical one. The phase diagrams including this intermediate state are plotted in coordinates of the magnitude and direction of elongation of the bottom layer.

High mobility single and few-layer graphene sheets are in many ways attractive as nanoelectronic circuit hosts but lack energy gaps, which are essential to the operation of field-effect transistors. One of the methods used to create gaps in the spectrum of graphene systems is to form long period moiré patterns by aligning the graphene and hexagonal boron nitride ( h-BN) substrate lattices. Here, we use planar tunneling devices with thin h-BN barriers to obtain direct and accurate tunneling spectroscopy measurements of the energy gaps in single-layer and bilayer graphene- h-BN superlattice structures at charge neutrality (first Dirac point) and at integer moiré band occupancies (second Dirac point, SDP) as a function of external electric and magnetic fields and the interface twist angle. In single-layer graphene, we find, in agreement with previous work, that gaps are formed at neutrality and at the hole-doped SDP, but not at the electron-doped SDP. Both primary and secondary gaps can be determined accurately by extrapolating Landau fan patterns to a zero magnetic field and are as large as ≈17 meV for devices in near-perfect alignment. For bilayer graphene, we find that gaps occur only at charge neutrality where they can be modified by an external electric field.

We study the electronic structure of superlattices consisting of graphene and hexagonal boron nitride slabs, using ab initio density functional theory. We find that the system favors a short C–B bond length at the interface between the two component materials. A sizeable band gap at the Dirac point is opened for superlattices with single graphene layers but not for superlattices with graphene bilayers. The system is promising for applications in electronic devices such as field effect transistors and metal-oxide semiconductors.

Hysteretic and nonlinear dielectric behaviour in ferroelectric ceramics has been of interest since 1950s, when these materials found application in various electronic devices. Presently, these phenomena concern with important areas of science, technology and engineering. In particular, nonlinearity and hysteresis are the key factors in performance, precision and accuracy of modern devices. Many theoretical and experimental studies have been aimed at understanding the origins of hysteresis and nonlinearity in ferroelectrics. Nowadays, there are several models that describe major contributions to nonlinearity and hysteresis on phenomenological, microscopical or statistical levels. These models have a limited area of applicability due to the complexity of physical processes occurring in real materials. Empirically, hysteresis and nonlinearity in ferroelectrics can be controlled by softening and hardening of the material. This is the case of most widely used ferroelectric, lead zirconate titanate (PZT). The soft compositions possess large electro-mechanical coefficients but also large hysteresis and nonlinearity while the opposite is true for the hard compositions. After fifty years since introduction of these materials, the mechanisms of softening and hardening remain poorly understood. The present study is aimed at a better understanding of the processes leading to hardening and softening of Pb(Zr,Ti)O3 ceramics in order to verify the key principles required for a more universal physical model of hysteresis and nonlinearity. Based on the present state of knowledge, such model should consider domain wall contribution to nonlinear and hysteretic polarization response and at the same time account for hardening and softening of the ferroelectric. For this purpose the well known lead zirconate titanate (PZT) ceramics doped with various concentrations of niobium (soft materials) or iron (hard materials) are chosen as a prototype of the ferroelectric system. The starting hypothesis of the thesis' approach is that the softening and hardening are a result of electrostatic arrangement of charged defects in the ceramic bulk: the hard materials are characterized by the ordered and the soft by disordered defects. The thesis then develops in detail the idea that hardening-softening transitions in a ferroelectric system may occur under the influence of (i) dopants, depending on their type and concentration, (ii) a cyclically applied electric field, (iii) a thermal treatment, and (iv) time. The transition from microscopic order to microscopic disorder is confirmed experimentally using carefully analyzed phenomenological parameters of the macroscopic hysteresis and nonlinearity. Among the nonlinear and hysteretic parameters characterizing the polarization response of a ferroelectric material, some (e.g., third harmonic of polarization) are shown to be particularly sensitive to the softness and hardness of ferroelectric system and thus may serve as the characteristics of ferroelectric hardening-softening transitions. Contribution of domain walls to hysteresis and nonlinearity is analyzed in terms of domain wall energy potential and degree of ordering of pinning centres. It is shown that two existing models characterizing hard (V-potential) and soft (random potential) materials are ideal, limiting cases and that some real materials are described by an intermediary case, which can evolve with time and under influence of external factors. The dielectric characterization performed at wide range of frequencies has revealed an increase of the apparent frequency dispersion of the dielectric permittivity with the transition from the hard to soft state in PZT ceramics. The investigation of dielectric response over a wide temperature range has revealed the profound presence of hopping conductivity in iron doped PZT ceramics below the Curie temperatures and its absence in niobium doped PZT ceramics. The role of hopping charged species in ferroelectric hardening – softening transitions is analyzed and discussed. The thesis is organized in the following way. A brief introduction (Chapter 1) and a literature review of the theoretical description of domain wall contribution to dielectric nonlinearity and hysteresis in ferroelectrics (Chapter 2) is followed by the thesis outline and discussion of a unified model of hysteresis and nonlinearity in ferroelectrics with ordered and disordered states of domain wall pinning centres (Chapter 3). Processing of ceramics is described in Chapter 4 and mathematical and experimental background for the dielectric spectroscopy study in Chapter 5. The results and discussion of detailed experimental studies of polarization response in ferroelectric PZT ceramics under subswitching and switching conditions are given in Chapters 6 and 7. The summary of the main results and conclusions are given in the last thesis section.

Fe intercalation under graphene and hexagonal boron nitride in-plane heterostructure on Pt(111)

In this paper, a two-dimensional phase field crystal model of graphene and hexagonal boron nitride (hBN) is extended to include out-of-plane deformations in stacked multilayer systems. As proof of principle, the model is shown analytically to reduce to standard models of flexible sheets in the small deformation limit. Applications to strained sheets, dislocation dipoles, and grain boundaries are used to validate the behavior of a single flexible graphene layer. For multilayer systems, parameters are obtained to match existing theoretical density functional theory calculations for graphene/graphene, hBN/hBN, and graphene/hBN bilayers. More precisely, it is shown that the parameters can be chosen to closely match the stacking energies and layer spacing calculated by Zhou et al. [Phys. Rev. B 92, 155438 (2015)]. Further validation of the model is presented in a study of rotated graphene bilayers and stacking boundaries. The flexibility of the model is illustrated by simulations that highlight the impact of complex microstructures in one layer on the other layer in a graphene/graphene bilayer.

Single-atom-embedded bilayer graphene and two-dimensional hexagonal boron nitride are proposed in terms of first-principles calculations. In particular, a series of 68 different single atoms are em...

The continuous scaling-down size of interconnects should be accompanied with ultra-thin diffusion barrier layers, which is used to suppress Cu diffusion into the dielectrics. Unfortunately, conventional barrier layers with thicknesses less than 4 nm fail to perform well. With the advent of 2D layered materials, graphene and hexagonal boron nitride have been proposed as alternative Cu diffusion barriers with thicknesses of ≈1 nm. However, defects such as vacancies may evolve into a Cu diffusion path, which is a challenging problem in design of diffusion barrier layers. The energy barrier of Cu atom diffused through a di-vacancy defect in graphene and hexagonal boron nitride is calculated by density functional theory. It is found that graphene offers higher energy barrier to Cu than hexagonal boron nitride. The higher energy barrier is attributed to the stronger interaction between Cu and C atoms in graphene as shown by charge density difference and Bader’s charge. Furthermore, we use the energy barriers of different vacancy structures and generate a dataset that will be used for machine learning. Our trained convolutional neural network is used to predict the energy barrier of Cu migration through randomly configured defected graphene and hexagonal boron nitride with $R^{2}$ of >99% for $4 \times 4$ supercell. These results provide guides on choosing between 2D materials as barrier layers, and applying deep learning to predict the 2D barrier performance.

Two-dimensional (2D) materials may enable a general approach to the introduction of a dipole at a semiconductor surface as well as control over other properties of the double layer at a semiconductor/liquid interface. Vastly different properties can be found in the 2D materials currently studied due in part to the range of the distribution of density-of-states. In this work, the open-circuit voltage (Voc) of p-Si-H, p-Si/Gr (graphene), and p-Si/h-BN (hexagonal boron nitride) in contact with a series of one-electron outer-sphere redox couples was investigated by macroscale measurements as well as by scanning electrochemical cell microscopy (SECCM). The band gaps of Gr and h-BN (0-5.97 eV) encompass the wide range of band gaps for 2D materials, so these interfaces (p-Si/Gr and p-Si/h-BN) serve as useful references to understand the behavior of 2D materials more generally. The value of Voc shifted with respect to the effective potential of the contacting solution, with slopes (ΔVoc/ΔEEff) of -0.27 and -0.38 for p-Si/Gr and p-Si/h-BN, respectively, indicating that band bending at the p-Si/h-BN and p-Si/Gr interfaces responds at least partially to changes in the electrochemical potential of the contacting liquid electrolyte. Additionally, SECCM is shown to be an effective method to interrogate the nanoscale photoelectrochemical behavior of an interface, showing little spatial variance over scales exceeding the grain size of the CVD-grown 2D materials in this work. The measurements demonstrated that the polycrystalline nature of the 2D materials had little effect on the results and confirmed that the macroscale measurements reflected the junction behavior at the nanoscale.

Two dimensional cubic boron nitride nanosheets converted from hexagonal boron nitride bilayers: electrical conductivity, magnetism and visible absorption properties

Single-layer and bilayer carbon and hexagonal boron nitride nanoscrolls as well as nanoscrolls made of bilayer graphene/hexagonal boron nitride heterostructure are considered. Structures of stable states of the corresponding nanoscrolls prepared by rolling single-layer and bilayer rectangular nanoribbons are obtained based on the analytical model and numerical calculations. The lengths of nanoribbons for which stable and energetically favorable nanoscrolls are possible are determined. Barriers to rolling of single-layer and bilayer nanoribbons into nanoscrolls and barriers to nanoscroll unrolling are calculated. Based on the calculated barriers nanoscroll lifetimes in the stable state are estimated. Elastic constants for bending of graphene and hexagonal boron nitride layers used in the model are found by density functional theory calculations.

When graphene is placed on hexagonal boron nitride with a twist angle, new properties develop due to the resulting moiré superlattice. Here, we report a method using Raman spectroscopy to make rapid, non-destructive measurements of the twist angle between bilayer graphene and hexagonal boron nitride. The lattice orientation is determined by using flakes with both bilayer and monolayer regions, and using the known Raman signature for the monolayer to measure the twist angle of the entire flake. The widths of the second order Raman peaks are found to vary linearly in the superlattice period and are used to determine the twist angle. The results are confirmed by using transport measurements to infer the superlattice period by the charge density required to reach the secondary resistance peaks. Small twist angles are also found to produce a significant modification of the first order Raman G band peak.

Ferroelectric materials exhibit important multifunctional electrical properties such as ferroelectric, dielectric, piezoelectric, pyroelectric, and electrooptic properties. They can be used to fabricate various microelectronic and optoelectric devices including nonvolatile ferroelectric random access memories, microsensors and microactuators, integrated capacitors, and electrooptic modulators [1-3]. Widely studied ferroelectric materials include Pb(Zr,Ti)O3 (PZT), lanthanide doped Bi4Ti3O12 (BiT), and BaTiO3. PZT is the most important piezoelectric material which has been used in various electronic devices. BaTiO3 and its solid solution with SrTiO3 exhibit high dielectric constant and other advantageous properties. Lanthanide doped BiT gained great interest on searching new ferroelectric thin films with fatigue-free polarization properties for non-volatile random access memories. Among them, La doped bismuth titanate and Nd-doped bismuth titanate exhibit excellent electrical properties such as high fatigue resistance, good retention, fast switching speed, high Curie temperature, large spontaneous polarization, and small coercive field [2-4]. In addition, lanthanide doped BiT do not contain lead, thus, environmental pollution and harm to health of human due to lead volatility in PZT can be avoided. Studies in the past decade indicate that lanthanide doped bismuth titanate ferroelectric thin films are the most promising candidate materials for nonvolatile ferroelectric random access memory applications. Most efforts have been devoted to improving the electrical properties of Bi4Ti3O12 (BIT) thin films by rare earth ion doping for the development of non-volatile ferroelectric random access memory applications [5-7]. It is worth pointing out that besides excellent ferroelectric polarization fatigue-free characteristics, the bismuth layered perovskite structure ferroelectric thin films also exhibit good piezoelectric properties and large optical nonlinearity [8-10]. Recently, photoluminescence (PL) properties originated from defects or rare earth ions in oxide ferroelectric materials have attracted much attention for possible integrated photoluminescent ferroelectric device applications. This paper briefly reviews the status and new progress on study of photoluminescence in low-dimensional oxide ferroelectric materials including ferroelectric thin films, nanopowders, nanorods or nanowires, and nanotubes, and some of our own research work in this field with an emphasis on the photoluminescence properties of lanthanide doped bismuth titanate thin films such as (Bi,Pr)4Ti3O12, (Bi,Eu)4Ti3O12, (Bi,Er)4Ti3O12, and codoped bismuth titanate thin films will be presented in this paper, also.

The coupling of ferroelectricity and magnetic order provides rich tunability for engineering material properties and demonstrates great potential for uncovering novel quantum phenomena and multifunctional devices. Here, we report interfacial ferroelectricity in moiré superlattices constructed from graphene and hexagonal boron nitride. We observe ferroelectric polarization in an across-layer moiré superlattice with an intercalated layer, demonstrating a remnant polarization comparable to its non-intercalated counterpart. Remarkably, we reveal a magnetic-field enhancement of ferroelectric polarization that persists up to room temperature, showcasing an unconventional amplification of ferroelectricity in materials lacking magnetic elements. This phenomenon, consistent across devices with varying layer configurations, arises purely from electronic rather than ionic contributions. Furthermore, the ferroelectric polarization in turn modulates quantum transport characteristics, suppressing Shubnikov-de Haas oscillations and altering quantum Hall states in polarized phases. This interplay between ferroelectricity and magneto-transport in non-magnetic materials is crucial for exploring magnetoelectric effects and advancing two-dimensional memory and logic applications.

Ternary two-dimensional (2D) materials such as fused graphene-boron nitride (GBN) nanosheets exhibit attractive physical and tunable properties far beyond their parent structures. Although these features impart several multifunctional properties in various matrices, a fundamental understanding on the nature of the interfacial interactions of these ternary 2D materials with host matrices and the role of their individual components has been elusive. Herein, we focus on intercalated GBN/ceramic composites as a model system and perform a series of density functional theory calculations to fill this knowledge gap. Propelled by more polarity and negative Gibbs free energy, our results demonstrate that GBN is more water-soluble than graphene and hexagonal boron nitride (h-BN), making it a preferred choice for slurry preparation and resultant intercalations. Further, a chief attribute of the intercalated GBN/ceramic is the formation of covalent C-O and B-O bonds between the two structures, changing the hybridization of GBN from sp2 to sp3. This change, combined with the electron release in the vicinity of the interfacial regions, leads to several nonintuitive mechanical and electrical alterations of the composite such as exhibiting higher young's modulus, strength, and ductility as well as sharp decline in the band gap. As a limiting case, though both tobermorite ceramic and h-BN are wide band gap materials, their intercalated composite becomes a p-type semiconductor, contrary to intuition. These multifunctional features, along with our fundamental electronic descriptions of the origin of property change, provide key guidelines for synthesizing next generation of multifunctional bilayer ceramics with remarkable properties on demand.