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At least 91 records · Page 5

Low-temperature processed beta-phase In 2 Se 3 ferroelectric semiconductor thin film transistors

As scaling becomes increasingly difficult, there is growing interest in vertical or three-dimensional stacking of transistors and especially memory. Ferroelectric semiconductor field effect transistors can be key enablers to improve energy efficiency and overall chip and memory performance. In this work, low-temperature processed, back-end-of-the-line compatible transistors were demonstrated by depositing a layered chalcogenide ferroelectric semiconductor, beta-phase In 2 Se 3 , at temperature as low as 400 °C. Top gate n-channel In 2 Se 3 thin film transistors were fabricated with field-effect mobility ∼1 cm 2 V −1 s −1 , and simple polarization switching based memory results are presented.

36 MATERIALS SCIENCE↗

Electrically controlled emission from singlet and triplet exciton species in atomically thin light-emitting diodes

We report electrically tunable spin singlet and triplet exciton emission from atomically aligned transition metal dichalcogenide (TMD) heterostructures. Furthermore, the observation of these states in both 0° and 60° heterostructures provides the stacking orientation degree of freedom for polarization switching in interlayer excitons. We confirm the spin configurations of the light-emitting excitons employing magnetic fields to measure effective exciton g factors. The interlayer tunneling current across the TMD heterostructure enables the electrical generation of singlet and triplet exciton emission in this atomically thin p-n junction. We demonstrate tunability between the singlet and triplet exciton photoluminescence via electrostatic gates and excitation power. By tuning the gates and interlayer bias voltage, the electroluminescence of the singlet and triplet can be switched with ratios of 10:1. Atomically thin TMD heterostructure light-emitting diodes thus enable a route for optoelectronic devices that can configure spin and valley quantum states independently.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Light-induced transitions of polar state and domain morphology of photoferroelectric nanoparticles

Using the Landau-Ginzburg-Devonshire approach, we study light-induced phase transitions, evolution of polar state and domain morphology in photo-ferroelectric nanoparticles (NPs). Light exposure increases the free carrier density near the NP surface and may in turn induce phase transitions from the nonpolar paraelectric to the polar ferroelectric phase. Using the uniaxial photo-ferroelectric Sn 2 P 2 S 6 as an example, here we show that visible light exposure induces the appearance and vanishing of striped, labyrinthine or curled domains and changes in the polarization switching hysteresis loop shape from paraelectric curves to double, pinched and single loops, as well as the shifting in the position of the tricritical point. Furthermore, we demonstrate that an ensemble of non-interacting photo-ferroelectric NPs may exhibit superparaelectric-like features at the tricritical point, such as strongly frequency-dependent giant piezoelectric and dielectric responses, which can potentially be exploited for piezoelectric applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Optical cycling on thorium monoxide for an improved test of fundamental symmetries

Optical cycling refers to repeated excitation and spontaneous emission on an electronic transition in an atom or molecule. Optical cycling in molecules can enable a wide range of quantum control and readout techniques, but unfortunately it has only been demonstrated on a small class of alkalilike or alkaline-earth-like molecules. Thorium monoxide (ThO), a molecule used in one of the most precise permanent electron electric dipole moment (eEDM) searches (ACME†) [Andreev et al., Nature (London) 562, 355 (2018)], does not fall into this category. In this work, we demonstrate the first optical cycling on this nonconventional class over a range of experimental parameter space, including laser intensity, polarization switching rate, and interaction time. We show that both the 𝐽 = 1 and 𝐽 = 2 rotational levels of ThO molecule are capable of cycling an average of 11(2) photons with a single laser, at scattering rates of 1.9⁢(6) × 10 6 and 2.3⁢(7) × 10 6 s −1 , respectively, before population is lost to other vibronic levels. We outline a scheme to apply this demonstrated optical cycling in an ACME-style eEDM measurement, improving the detection efficiency by over fourfold compared to noncycling fluorescence detection. This would lead to over a twofold enhancement in the statistical sensitivity of the eEDM search. This optical-cycling scheme can be further extended to scatter ∼100 photons, which would enable a wider range of quantum control and sensing using ThO molecules.

Atomic & molecular processes in external fields↗

Emergent ferroelectricity in subnanometer binary oxide films on silicon

The critical size limit of voltage-switchable electric dipoles has extensive implications for energy-efficient electronics, underlying the importance of ferroelectric order stabilized at reduced dimensionality. Here, we report on the thickness-dependent antiferroelectric-to-ferroelectric phase transition in zirconium dioxide (ZrO 2 ) thin films on silicon. The emergent ferroelectricity and hysteretic polarization switching in ultrathin ZrO 2 , conventionally a paraelectric material, notably persists down to a film thickness of 5 angstroms, the fluorite-structure unit-cell size. This approach to exploit three-dimensional centrosymmetric materials deposited down to the two-dimensional thickness limit, particularly within this model fluorite-structure system that possesses unconventional ferroelectric size effects, offers substantial promise for electronics, demonstrated by proof-of-principle atomic-scale nonvolatile ferroelectric memory on silicon. Additionally, it is also indicative of hidden electronic phenomena that are achievable across a wide class of simple binary materials.

42 ENGINEERING↗

Emergent Ferroelectric Switching Behavior from Polar Vortex Lattice

We report topologically protected polar textures have provided a rich playground for the exploration of novel, emergent phenomena. Recent discoveries indicate that ferroelectric vortices and skyrmions not only host properties markedly different from traditional ferroelectrics, but also that these properties can be harnessed for unique memory devices. Using a combination of capacitor-based capacitance measurements and computational models, it is demonstrated that polar vortices in dielectric–ferroelectric–dielectric trilayers exhibit classical ferroelectric bi-stability together with the existence of low-field metastable polarization states. This behavior is directly tied to the in-plane vortex ordering, and it is shown that it can be used as a new method of non-destructive readout-out of the poled state.

36 MATERIALS SCIENCE↗

Ferroelectric Switching of Pure Spin Polarization in Two-Dimensional Electron Gas

Two-dimensional electron gas (2DEG) created at compound interfaces can exhibit a broad range of exotic physical phenomena, including quantum Hall phase, emergent ferromagnetism, and superconductivity. Although electron spin plays key roles in these phenomena, the fundamental understanding and application prospects of such emergent interfacial states have been largely impeded by the lack of purely spin-polarized 2DEG. In this paper, by first-principles calculations of the multiferroic superlattice GeTe/MnTe, we find the ferroelectric polarization of GeTe is concurrent with the half-metallic 2DEG at interfaces. Remarkably, the pure spin polarization of the 2DEG can be created and annihilated by polarizing and depolarizing the ferroelectrics and can be switched (between pure spin-up and pure spin-down) by flipping the ferroelectric polarization. Given the electric-field amplification effect of ferroelectric electronics, we envision multiferroic superlattices could open up new opportunities for low-power, high-efficiency spintronic devices such as spin field-effect transistors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Switching of Hybrid Improper Ferroelectricity in Oxide Double Perovskites

In ABO 3 -type perovskite oxides with Pnma symmetry, rotation (Q R+ , a 0 a 0 c + ) and tilt (Q T , a – a – c 0 ) of BO 6 octahedra are the two primary order parameters. These order parameters establish an inherent trilinear coupling with anti-ferroelectric A-site displacement (Q AFE ) to form the low-symmetry phase. The symmetry is further lowered in double perovskite oxides (DPOs) due to A/A' cation ordering. It in turn makes these systems polar via hybrid improper ferroelectric mechanism, primarily driven by Q R+ and Q T . Naturally, it has been believed that functionalities such as polarization can also be switched by tuning these primary order parameters. However, mystery around finding switching mechanism still remains. Our study based on density functional theory calculations combined with finite-temperature molecular dynamics simulations shows that the polarization switching is a two-step process, driven by out-of-phase rotation (Q R– , a 0 a 0 c – when Q T = 0 or, a – a – b – when Q T ≠ 0). A series of polar DPOs such as KLnFeOsO 6 [Ln = Sm, Gd, Dy, Tm (lanthanides) and Y (rare earth)], all belonging to P2 1 symmetry, are considered in this investigation. The polarization switching P ($\overrightarrow{P}$) occurs at a very high temperature of ~1150 K through a phase transition, from a polar (P2 1 ) phase with $\overrightarrow{P}$(+) to $\overrightarrow{P}$(-) via a non-polar P4/n phase. The switching itself is metastable in nature. The switching (both polarization and spin state) is only observed for a very short period of time (~23 ps) that poses limitation on using such a mechanism in memory device realization. We demonstrate a concurrent heating–cooling procedure to overcome such shortcoming. In conclusion, simulations conducted at 600 K further imply that long lasting switching can be achieved, at least for 1.2 ns for 600 K, and ideally for an infinite time, if the material is heated just above the T c followed by rapid cooling to a temperature below T c .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sub-10 nm Probing of Ferroelectricity in Heterogeneous Materials by Machine Learning Enabled Contact Kelvin Probe Force Microscopy

Reducing the dimensions of ferroelectric materials down to the nanoscale has strong implications on the ferroelectric polarization pattern and on the ability to switch the polarization. As the size of ferroelectric domains shrinks to the nanometer scale, the heterogeneity of the polarization pattern becomes increasingly pronounced, enabling a large variety of possible polar textures in nanocrystalline and nanocomposite materials. Critical to the understanding of fundamental physics of such materials and hence their applications in electronic nanodevices is the ability to investigate their ferroelectric polarization at the nanoscale in a nondestructive way. We show that contact Kelvin probe force microscopy (cKPFM) combined with a k-means response clustering algorithm enables to measure the ferroelectric response at a mapping resolution of 8 nm. In a BaTiO 3 thin film on silicon composed of tetragonal and hexagonal nanocrystals, we determine a nanoscale lateral distribution of discrete ferroelectric response clusters, fully consistent with the nanostructure determined by transmission electron microscopy. Moreover, we apply this data clustering method to the cKPFM responses measured at different temperatures, which allows us to follow the corresponding change in the polarization pattern as the Curie temperature is approached and across the phase transition. This work opens up perspectives for mapping complex ferroelectric polarization textures such as curled/swirled polar textures that can be stabilized in epitaxial heterostructures and more generally for mapping the polar domain distribution of any spatially highly heterogeneous ferroelectric materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unconventional crystal-field splitting in noncentrosymmetric BaTiO 3 thin films

Understanding the crystal-field splitting and orbital polarization in noncentrosymmetric systems such as ferroelectric materials is fundamentally important. In this work, taking BaTiO 3 as a representative material, we investigate titanium crystal-field splitting and orbital polarization in noncentrosymmetric TiO 6 octahedra with resonant x-ray linear dichroism at the Ti L 2,3 edge. The high-quality BaTiO 3 thin films were deposited on DyScO 3 (110) single crystal substrates in a layer-by-layer way by pulsed laser deposition. The reflection high-energy electron diffraction and element specific x-ray absorption spectroscopy were performed to characterize the structural and electronic properties of the films. In sharp contrast to conventional crystal-field splitting and orbital configuration (d xz /d yz < d xy < d 3z 2 -r 2 < d x 2 -y 2 or d xy < d xz /d yz < d x 2 -y 2 < d 3z 2 -r 2 ) expected from compressive or tensile epitaxial strain, respectively, it is revealed that d xz , d yz , and d xy orbitals are nearly degenerate, whereas d 3z 2 -r 2 and d x 2 -y 2 orbitals are split with an energy gap ~100 meV in the epitaxial BaTiO 3 films. We find that the unexpected degenerate orbitals d xz /d yz /d xy result from the competition between the orbital splitting induced by epitaxial strain and that induced by polar distortions of BaTiO 3 films. Our results provide a route to manipulate orbital degree of freedom by switching electric polarization in ferroelectric materials.

36 MATERIALS SCIENCE↗

Wake up and retention in zinc magnesium oxide ferroelectric films

Zn 0.64 Mg 0.36 O (ZMO) is a newly discovered ferroelectric oxide with the wurtzite structure. Epitaxial Zn 0.64 Mg 0.36 O films from 0.036 to 0.5 μm in thickness are grown on Pt/sapphire with the crystallographic c-axis out of plane. At room temperature, the remanent polarization is ~80 μC/cm 2 and the coercive field is ~3 MV/cm. The coercive field is strongly temperature dependent up to 240 °C with a pseudo-activation energy of 23 ± 0.3 meV, suggesting that polarization reversal occurs through an extrinsic process such as domain wall motion. ZMO films can be woken up in 20 electric field cycles on driving near the coercive field; they wake up in a single loop at fields in excess of 4 MV/cm. A thermally activated fluid imprint process, with a pseudo-activation energy of 67 ± 8 meV, enlarges the coercive field by several hundred kV cm –1 after switching the polarization. Additionally, ZMO films exhibit excellent retention characteristics; no reduction in the polarization is observed up to 1000 h from room temperature to 200 °C bakes. Here, this current early generation of ZMO films can survive several thousand switching cycles before dielectric breakdown occurs.

36 MATERIALS SCIENCE↗

Releasing chemical energy in spatiallyprogrammed ferroelectrics

Chemical energy ferroelectrics are generally solid macromolecules showing spontaneous polarization and chemical bonding energy. These materials still suffer drawbacks, including the limited control of energy release rate, and thermal decomposition energy well below total chemical energy. To overcome these drawbacks, we report the integrated molecular ferroelectric and energetic material from machine learning-directed additive manufacturing coupled with the ice-templating assembly. The resultant aligned porous architecture shows a low density of 0.35 g cm -3 , polarization-controlled energy release, and an anisotropic thermal conductivity ratio of 15. Thermal analysis suggests that the chlorine radicals react with macromolecules enabling a large exothermic enthalpy of reaction (6180 kJ kg -1 ). In addition, the estimated detonation velocity of molecular ferroelectrics can be tuned from 6.69 ± 0.21 to 7.79 ± 0.25 km s -1 by switching the polarization state. These results provide a pathway toward spatially programmed energetic ferroelectrics for controlled energy release rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optically and thermally driven huge lattice orbital and spin angular momenta from spinning fullerenes

Lattice vibration in solids may carry angular momentum. But unlike the intrinsic spin of electrons, the lattice vibration is rarely rotational. To induce angular momentum, one needs to find a material that can accommodate a twisted normal mode, two orthogonal modes, or excitation of magnons. If excitation is too strong, one may exceed the Lindemann limit, so the material melts. Therefore these methods are not ideal. Here, we theoretically propose a route to phonon angular momentum in a molecular crystal C 60 . We find that a single laser pulse is able to inject a significant amount of angular momentum to C 60 , and the momentum transfer is helicity dependent. Changing from right-circularly polarized light to left-circularly polarized light switches the direction of phonon angular momentum. On the ultrafast timescale, the orbital angular momentum change closely resembles the displacive excitation of coherent phonons, with a cosine-function dependence on time, different from the spin counterpart. Atomic displacements, even under strong laser excitation, remain far below the Lindemann criterion. Under thermal excitation, spinning C 60 even at room temperature generates a huge angular momentum close to several hundred h¯. Our finding opens the door to a large group of fullerenes, from C 60 , C 70 to their endohedral derivatives, where angular momentum can be generated through light or temperature. Furthermore, this paves the way to the phononic control electronic spin and harvesting thermal energy through phonon angular momentum.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The Third Dimension of Ferroelectric Domain Walls

Abstract Ferroelectric domain walls are quasi‐2D systems that show great promise for the development of nonvolatile memory, memristor technology, and electronic components with ultrasmall feature size. Electric fields, for example, can change the domain wall orientation relative to the spontaneous polarization and switch between resistive and conductive states, controlling the electrical current. Being embedded in a 3D material, however, the domain walls are not perfectly flat and can form networks, which leads to complex physical structures. In this work, the importance of the nanoscale structure for the emergent transport properties is demonstrated, studying electronic conduction in the 3D network of neutral and charged domain walls in ErMnO 3 . By combining tomographic microscopy techniques and finite element modeling, the contribution of domain walls within the bulk is clarified and the significance of curvature effects for the local conduction is shown down to the nanoscale. The findings provide insights into the propagation of electrical currents in domain wall networks, reveal additional degrees of freedom for their control, and provide quantitative guidelines for the design of domain‐wall‐based technology.

36 MATERIALS SCIENCE↗

Remote surface optical phonon scattering in ferroelectric Ba 0.6 Sr 0.4 TiO 3 gated graphene

We report the effect of remote surface optical (RSO) phonon scattering on carrier mobility in monolayer graphene gated by ferroelectric oxide. We fabricate monolayer graphene transistors back-gated by epitaxial (001) Ba 0.6 Sr 0.4 TiO 3 films, with field effect mobility up to 23 000 cm 2 V –1 s –1 achieved. Switching ferroelectric polarization induces nonvolatile modulation of resistance and quantum Hall effect in graphene at low temperatures. Ellipsometry spectroscopy studies reveal four pairs of optical phonon modes in Ba 0.6 Sr 0.4 TiO 3 , from which we extract RSO phonon frequencies. The temperature dependence of resistivity in graphene can be well accounted for by considering the scattering from the intrinsic longitudinal acoustic phonon and the RSO phonon, with the latter dominated by the mode at 35.8 meV. Furthermore, our study reveals the room temperature mobility limit of ferroelectric-gated graphene transistors imposed by RSO phonon scattering.

36 MATERIALS SCIENCE↗

Polarization and domains in wurtzite ferroelectrics: Fundamentals and applications

The 2019 report of ferroelectricity in (Al,Sc)N [Fichtner et al., J. Appl. Phys. 125, 114103 (2019)] broke a long-standing tradition of considering AlN the textbook example of a polar but non-ferroelectric material. Combined with the recent emergence of ferroelectricity in HfO2-based fluorites [Böscke et al., Appl. Phys. Lett. 99, 102903 (2011)], these unexpected discoveries have reinvigorated studies of integrated ferroelectrics, with teams racing to understand the fundamentals and/or deploy these new materials—or, more correctly, attractive new capabilities of old materials—in commercial devices. The five years since the seminal report of ferroelectric (Al,Sc)N [Fichtner et al., J. Appl. Phys. 125, 114103 (2019)] have been particularly exciting, and several aspects of recent advances have already been covered in recent review articles [Jena et al., Jpn. J. Appl. Phys. 58, SC0801 (2019); Wang et al., Appl. Phys. Lett. 124, 150501 (2024); Kim et al., Nat. Nanotechnol. 18, 422–441 (2023); and F. Yang, Adv. Electron. Mater. 11, 2400279 (2024)]. We focus here on how the ferroelectric wurtzites have made the field rethink domain walls and the polarization reversal process—including the very character of spontaneous polarization itself—beyond the classic understanding that was based primarily around perovskite oxides and extended to other chemistries with various caveats. The tetrahedral and highly covalent bonding of AlN along with the correspondingly large bandgap lead to fundamental differences in doping/alloying, defect compensation, and charge distribution when compared to the classic ferroelectric systems; combined with the unipolar symmetry of the wurtzite structure, the result is a class of ferroelectrics that are both familiar and puzzling, with characteristics that seem to be perfectly enabling and simultaneously nonstarters for modern integrated devices. The goal of this review is to (relatively) quickly bring the reader up to speed on the current—at least as of early 2025—understanding of domains and defects in wurtzite ferroelectrics, covering the most relevant work on the fundamental science of these materials as well as some of the most exciting work in early demonstrations of device structures.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Ionic Control over Ferroelectricity in 2D Layered van der Waals Capacitors

The van der Waals layered material CuInP 2 S 6 features interesting functional behavior, including the existence of four uniaxial polarization states, polarization reversal against the electric field through Cu ion migration, a negative-capacitance regime, and reversible extraction of Cu ions. At the heart of these characteristics lies the high mobility of Cu ions, which also determines the spontaneous polarization. Therefore, Cu migration across the lattice results in unusual ferroelectric behavior. Here, we demonstrate how the interplay of polar and ionic properties provides a path to ionically controlled ferroelectric behavior, achieved by applying selected DC voltage pulses and subsequently probing ferroelectric switching during fast triangular voltage sweeps. Using current measurements and theoretical calculations, we observe that increasing DC pulse duration results in higher ionic currents, the buildup of an internal electric field that shifts polarization loops, and an increase in total switchable polarization by ~50% due to the existence of a high polarization phase which is stabilized by the internal electric field. Apart from tuning ferroelectric behavior by selected square pulses, hysteretic polarization switching can even be entirely deactivated and reactivated, resulting in three-state systems where polarization switching is either inhibited or can be performed in two different directions.

36 MATERIALS SCIENCE↗