Although only a few 2D materials have been predicted to possess ferroelectricity, 2D ferroelectrics are expected to play a dominant role in the upcoming nano era as important functional materials. The ferroelectric properties of 2D ferroelectrics are significantly different than those of traditional bulk ferroelectrics owing to their intrinsic size and surface effects. To date, 2D ferroelectrics have been reported to exhibit diverse properties ranging from bulk photovoltaic and piezoelectric/pyroelectric effects to the spontaneous valley and spin polarization. These properties are either dependent on ferroelectric polarization or coupled with it for easy electric control, thus making 2D ferroelectrics applicable to multifunctional nanodevices. At present, cumulative efforts are being made to explore 2D ferroelectrics in theories, experiments, and applications. Herein, such theories and methods are briefly introduced. Subsequently, intrinsic and extrinsic origins of 2D ferroelectricity are separately summarized. In addition, invented or laboratory-validated 2D ferroelectric-based applications are listed. Finally, the existing challenges and prospects of 2D ferroelectrics are discussed.

Review on Recent Developments in 2D Ferroelectrics: Theories and Applications.

A grand family of two-dimensional (2D) materials and their heterostructures have been discovered through the extensive experimental and theoretical efforts of chemists, material scientists, physicists, and technologists. These pioneering works contribute to realizing the fundamental platforms to explore and analyze new physical/chemical properties and technological phenomena at the micro-nano-pico scales. Engineering 2D van der Waals (vdW) materials and their heterostructures via chemical and physical methods with a suitable choice of stacking order, thickness, and interlayer interactions enable exotic carrier dynamics, showing potential in high-frequency electronics, broadband optoelectronics, low-power neuromorphic computing, and ubiquitous electronics. This comprehensive review addresses recent advances in terms of representative 2D materials, the general fabrication methods, and characterization techniques and the vital role of the physical parameters affecting the quality of 2D heterostructures. The main emphasis is on 2D heterostructures and 3D-bulk (3D) hybrid systems exhibiting intrinsic quantum mechanical responses in the optical, valley, and topological states. Finally, we discuss the universality of 2D heterostructures with representative applications and trends for future electronics and optoelectronics (FEO) under the challenges and opportunities from physical, nanotechnological, and material synthesis perspectives.

2D Heterostructures for Ubiquitous Electronics and Optoelectronics: Principles, Opportunities, and Challenges.

Copper indium thiophosphate, CuInP2S6, has attracted much attention in recent years due to its van der Waals layered structure and robust ferroelectricity at room temperature. In this review, we aim to give an overview of the various properties of CuInP2S6, covering structural, ferroelectric, dielectric, piezoelectric and transport properties, as well as its potential applications. We also highlight the remaining questions and possible research directions related to this fascinating material and other compounds of the same family.

Van der Waals layered ferroelectric CuInP 2 S 6 : Physical properties and device applications

Polar van der Waals chalcogenophosphates exhibit unique properties, such as negative electrostriction and multi-well ferrielectricity, and enable combining dielectric and 2D electronic materials. Using low temperature piezoresponse force microscopy, we revealed coexistence of piezoelectric and non-piezoelectric phases in CuInP2Se6, forming unusual domain walls with enhanced piezoelectric response. From systematic imaging experiments we have inferred the formation of a partially polarized antiferroelectric state, with inclusions of structurally distinct ferrielectric domains enclosed by the corresponding phase boundaries. The assignment is strongly supported by optical spectroscopies and density-functional-theory calculations. Enhanced piezoresponse at the ferrielectric/antiferroelectric phase boundary and the ability to manipulate this entity with electric field on the nanoscale expand the existing phenomenology of functional domain walls. At the same time, phase-coexistence in chalcogenophosphates may lead to rational strategies for incorporation of ferroic functionality into van der Waals heterostructures, with stronger resilience toward detrimental size-effects. Domain walls in van der Waals layered ferrielectric CuInP2Se6 exhibit piezoelectric response. This striking departure from traditional ferroelectric behavior is ascribed to a partially polarized antiferroelectric state, where the domain wall separates coexisting regions of ferrielectric and antiferroelectric phases.

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Piezoelectric domain walls in van der Waals antiferroelectric CuInP2Se6.

The ABINIT software project

The family of layered thio- and seleno-phosphates has gained attention as potential control dielectrics for the rapidly growing family of two-dimensional and quasi-two-dimensional electronic materials. Here we report a combination of density functional theory calculations, quantum molecular dynamics simulations and variable-temperature, -pressure and -bias piezoresponse force microscopy data to predict and verify the existence of an unusual ferroelectric property—a uniaxial quadruple potential well for Cu displacements—enabled by the van der Waals gap in copper indium thiophosphate (CuInP2S6). The calculated potential energy landscape for Cu displacements is strongly influenced by strain, accounting for the origin of the negative piezoelectric coefficient and rendering CuInP2S6 a rare example of a uniaxial multi-well ferroelectric. Experimental data verify the coexistence of four polarization states and explore the temperature-, pressure- and bias-dependent piezoelectric and ferroelectric properties, which are supported by bias-dependent molecular dynamics simulations. These phenomena offer new opportunities for both fundamental studies and applications in data storage and electronics. The atomic displacements that generate ferroelectricity in materials commonly fit a double-well potential energy surface. Here, ferroelectricity in two-dimensional CuInP2S6 is shown to fit a quadruple well due to the van der Waals gap between layers of this material.

Marius Chyasnavichus

Papers

Tunable quadruple-well ferroelectric van der Waals crystals.