Giant energy storage and power density negative capacitance superlattices.

Dielectric electrostatic capacitors1, because of their ultrafast charge-discharge, are desirable for high-power energy storage applications. Along with ultrafast operation, on-chip integration can enable miniaturized energy storage devices for emerging autonomous microelectronics and microsystems2-5. Moreover, state-of-the-art miniaturized electrochemical energy storage systems-microsupercapacitors and microbatteries-currently face safety, packaging, materials and microfabrication challenges preventing on-chip technological readiness2,3,6, leaving an opportunity for electrostatic microcapacitors. Here we report record-high electrostatic energy storage density (ESD) and power density, to our knowledge, in HfO2-ZrO2-based thin film microcapacitors integrated into silicon, through a three-pronged approach. First, to increase intrinsic energy storage, atomic-layer-deposited antiferroelectric HfO2-ZrO2 films are engineered near a field-driven ferroelectric phase transition to exhibit amplified charge storage by the negative capacitance effect7-12, which enhances volumetric ESD beyond the best-known back-end-of-the-line-compatible dielectrics (115 J cm-3) (ref. 13). Second, to increase total energy storage, antiferroelectric superlattice engineering14 scales the energy storage performance beyond the conventional thickness limitations of HfO2-ZrO2-based (anti)ferroelectricity15 (100-nm regime). Third, to increase the storage per footprint, the superlattices are conformally integrated into three-dimensional capacitors, which boosts the areal ESD nine times and the areal power density 170 times that of the best-known electrostatic capacitors: 80 mJ cm-2 and 300 kW cm-2, respectively. This simultaneous demonstration of ultrahigh energy density and power density overcomes the traditional capacity-speed trade-off across the electrostatic-electrochemical energy storage hierarchy1,16. Furthermore, the integration of ultrahigh-density and ultrafast-charging thin films within a back-end-of-the-line-compatible process enables monolithic integration of on-chip microcapacitors5, which can unlock substantial energy storage and power delivery performance for electronic microsystems17-19.

Ultrathin ferroic HfO2-ZrO2 superlattice gate stack for advanced transistors.

With the scaling of lateral dimensions in advanced transistors, an increased gate capacitance is desirable both to retain the control of the gate electrode over the channel and to reduce the operating voltage1. This led to a fundamental change in the gate stack in 2008, the incorporation of high-dielectric-constant HfO2 (ref. 2), which remains the material of choice to date. Here we report HfO2-ZrO2 superlattice heterostructures as a gate stack, stabilized with mixed ferroelectric-antiferroelectric order, directly integrated onto Si transistors, and scaled down to approximately 20 ångströms, the same gate oxide thickness required for high-performance transistors. The overall equivalent oxide thickness in metal-oxide-semiconductor capacitors is equivalent to an effective SiO2 thickness of approximately 6.5 ångströms. Such a low effective oxide thickness and the resulting large capacitance cannot be achieved in conventional HfO2-based high-dielectric-constant gate stacks without scavenging the interfacial SiO2, which has adverse effects on the electron transport and gate leakage current3. Accordingly, our gate stacks, which do not require such scavenging, provide substantially lower leakage current and no mobility degradation. This work demonstrates that ultrathin ferroic HfO2-ZrO2 multilayers, stabilized with competing ferroelectric-antiferroelectric order in the two-nanometre-thickness regime, provide a path towards advanced gate oxide stacks in electronic devices beyond conventional HfO2-based high-dielectric-constant materials.

Publisher Correction: Enhanced ferroelectricity in ultrathin films grown directly on silicon.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Enhanced ferroelectricity in ultrathin films grown directly on silicon.

Ultrathin ferroelectric materials could potentially enable low-power perovskite ferroelectric tetragonality logic and nonvolatile memories1,2. As ferroelectric materials are made thinner, however, the ferroelectricity is usually suppressed. Size effects in ferroelectrics have been thoroughly investigated in perovskite oxides-the archetypal ferroelectric system3. Perovskites, however, have so far proved unsuitable for thickness scaling and integration with modern semiconductor processes4. Here we report ferroelectricity in ultrathin doped hafnium oxide (HfO2), a fluorite-structure oxide grown by atomic layer deposition on silicon. We demonstrate the persistence of inversion symmetry breaking and spontaneous, switchable polarization down to a thickness of one nanometre. Our results indicate not only the absence of a ferroelectric critical thickness but also enhanced polar distortions as film thickness is reduced, unlike in perovskite ferroelectrics. This approach to enhancing ferroelectricity in ultrathin layers could provide a route towards polarization-driven memories and ferroelectric-based advanced transistors. This work shifts the search for the fundamental limits of ferroelectricity to simpler transition-metal oxide systems-that is, from perovskite-derived complex oxides to fluorite-structure binary oxides-in which 'reverse' size effects counterintuitively stabilize polar symmetry in the ultrathin regime.

Manipulating chiral spin transport with ferroelectric polarization.

A magnon is a collective excitation of the spin structure in a magnetic insulator and can transmit spin angular momentum with negligible dissipation. This quantum of a spin wave has always been manipulated through magnetic dipoles (that is, by breaking time-reversal symmetry). Here we report the experimental observation of chiral spin transport in multiferroic BiFeO3 and its control by reversing the ferroelectric polarization (that is, by breaking spatial inversion symmetry). The ferroelectrically controlled magnons show up to 18% modulation at room temperature. The spin torque that the magnons in BiFeO3 carry can be used to efficiently switch the magnetization of adjacent magnets, with a spin-torque efficiency comparable to the spin Hall effect in heavy metals. Utilizing such controllable magnon generation and transmission in BiFeO3, an all-oxide, energy-scalable logic is demonstrated composed of spin-orbit injection, detection and magnetoelectric control. Our observations open a new chapter of multiferroic magnons and pave another path towards low-dissipation nanoelectronics.

Author Correction: Spatially resolved steady-state negative capacitance.

In this Letter, the first name of author Bhagwati Prasad was misspelled Bhagawati. This error has been corrected online.

Spatially resolved steady-state negative capacitance.

Negative capacitance is a newly discovered state of ferroelectric materials that holds promise for electronics applications by exploiting a region of thermodynamic space that is normally not accessible1-14. Although existing reports of negative capacitance substantiate the importance of this phenomenon, they have focused on its macroscale manifestation. These manifestations demonstrate possible uses of steady-state negative capacitance-for example, enhancing the capacitance of a ferroelectric-dielectric heterostructure4,7,14 or improving the subthreshold swing of a transistor8-12. Yet they constitute only indirect measurements of the local state of negative capacitance in which the ferroelectric resides. Spatial mapping of this phenomenon would help its understanding at a microscopic scale and also help to achieve optimal design of devices with potential technological applications. Here we demonstrate a direct measurement of steady-state negative capacitance in a ferroelectric-dielectric heterostructure. We use electron microscopy complemented by phase-field and first-principles-based (second-principles) simulations in SrTiO3/PbTiO3 superlattices to directly determine, with atomic resolution, the local regions in the ferroelectric material where a state of negative capacitance is stabilized. Simultaneous vector mapping of atomic displacements (related to a complex pattern in the polarization field), in conjunction with reconstruction of the local electric field, identify the negative capacitance regions as those with higher energy density and larger polarizability: the domain walls where the polarization is suppressed.

In-Situ Measurement of Magnetoelectric Coupling and Strain Transfer in Multiferroic Nanocomposites of CoFe2O4 and Hf0.5Zr0.5O2 with Residual Porosity.

With increasing applications for voltage-controlled magnetism, the need to more fully understand magnetoelectric coupling and strain transfer in nanostructured multiferroic composites has also increased. Here, multiferroic nanocomposites were synthesized using block copolymer templating to create mesoporous cobalt ferrite (CFO), followed by partly filling the pores with ferroelectric zirconium-substituted hafnia (HZO) using atomic layer deposition (ALD) to produce a porous multiferroic composite with enhanced mechanical flexibility. Upon electrical poling of the nanocomposite, we observed large changes in the magnetization. These changes partly relaxed upon removing the electric field, suggesting a strain-mediated mechanism. Both the anisotropic strain transfer from HZO to CFO and the strain relaxation after the field was removed were confirmed using high-resolution X-ray diffraction measurements collected during in-situ poling. The in-situ observation of both anisotropic strain transfer and large magnetization changes allows us to directly characterize the strong multiferroic coupling that can occur in flexible, nanostructured composites.

Switching of perpendicularly polarized nanomagnets with spin orbit torque without an external magnetic field by engineering a tilted anisotropy.

Spin orbit torque (SOT) provides an efficient way to significantly reduce the current required for switching nanomagnets. However, SOT generated by an in-plane current cannot deterministically switch a perpendicularly polarized magnet due to symmetry reasons. On the other hand, perpendicularly polarized magnets are preferred over in-plane magnets for high-density data storage applications due to their significantly larger thermal stability in ultrascaled dimensions. Here, we show that it is possible to switch a perpendicularly polarized magnet by SOT without needing an external magnetic field. This is accomplished by engineering an anisotropy in the magnets such that the magnetic easy axis slightly tilts away from the direction, normal to the film plane. Such a tilted anisotropy breaks the symmetry of the problem and makes it possible to switch the magnet deterministically. Using a simple Ta/CoFeB/MgO/Ta heterostructure, we demonstrate reversible switching of the magnetization by reversing the polarity of the applied current. This demonstration presents a previously unidentified approach for controlling nanomagnets with SOT.

Sustained Sub-60 mV/decade Switching via the Negative Capacitance Effect in MoS2 Transistors.

It has been shown that a ferroelectric material integrated into the gate stack of a transistor can create an effective negative capacitance (NC) that allows the device to overcome "Boltzmann tyranny". While this switching below the thermal limit has been observed with Si-based NC field-effect transistors (NC-FETs), the adaptation to 2D materials would enable a device that is scalable in operating voltage as well as size. In this work, we demonstrate sustained sub-60 mV/dec switching, with a minimum subthreshold swing (SS) of 6.07 mV/dec (average of 8.03 mV/dec over 4 orders of magnitude in drain current), by incorporating hafnium zirconium oxide (HfZrO2 or HZO) ferroelectric into the gate stack of a MoS2 2D-FET. By first fabricating and characterizing metal-ferroelectric-metal capacitors, the MoS2 is able to be transferred directly on top and characterized with both a standard and a negative capacitance gate stack. The 2D NC-FET exhibited marked enhancement in low-voltage switching behavior compared to the 2D-FET on the same MoS2 channel, reducing the SS by 2 orders of magnitude. A maximum internal voltage gain of ∼28× was realized with ∼12 nm thick HZO. Several unique dependencies were observed, including threshold voltage (Vth) shifts in the 2D NC-FET (compared to the 2D-FET) that correlate with source/drain overlap capacitance and changes in HZO (ferroelectric) and HfO2 (dielectric) thicknesses. Remarkable sub-60 mV/dec switching was obtained from 2D NC-FETs of various sizes and gate stack thicknesses, demonstrating great potential for enabling size- and voltage-scalable transistors.

Interface Engineering of Domain Structures in BiFeO3 Thin Films.

A wealth of fascinating phenomena have been discovered at the BiFeO3 domain walls, examples such as domain wall conductivity, photovoltaic effects, and magnetoelectric coupling. Thus, the ability to precisely control the domain structures and accurately study their switching behaviors is critical to realize the next generation of novel devices based on domain wall functionalities. In this work, the introduction of a dielectric layer leads to the tunability of the depolarization field both in the multilayers and superlattices, which provides a novel approach to control the domain patterns of BiFeO3 films. Moreover, we are able to study the switching behavior of the first time obtained periodic 109° stripe domains with a thick bottom electrode. Besides, the precise controlling of pure 71° and 109° periodic stripe domain walls enable us to make a clear demonstration that the exchange bias in the ferromagnet/BiFeO3 system originates from 109° domain walls. Our findings provide future directions to study the room temperature electric field control of exchange bias and open a new pathway to explore the room temperature multiferroic vortices in the BiFeO3 system.

Negative capacitance in a ferroelectric capacitor.

The Boltzmann distribution of electrons poses a fundamental barrier to lowering energy dissipation in conventional electronics, often termed as Boltzmann Tyranny. Negative capacitance in ferroelectric materials, which stems from the stored energy of a phase transition, could provide a solution, but a direct measurement of negative capacitance has so far been elusive. Here, we report the observation of negative capacitance in a thin, epitaxial ferroelectric film. When a voltage pulse is applied, the voltage across the ferroelectric capacitor is found to be decreasing with time--in exactly the opposite direction to which voltage for a regular capacitor should change. Analysis of this 'inductance'-like behaviour from a capacitor presents an unprecedented insight into the intrinsic energy profile of the ferroelectric material and could pave the way for completely new applications.

Ultrathin compound semiconductor on insulator layers for high-performance nanoscale transistors.

Over the past several years, the inherent scaling limitations of silicon (Si) electron devices have fuelled the exploration of alternative semiconductors, with high carrier mobility, to further enhance device performance. In particular, compound semiconductors heterogeneously integrated on Si substrates have been actively studied: such devices combine the high mobility of III-V semiconductors and the well established, low-cost processing of Si technology. This integration, however, presents significant challenges. Conventionally, heteroepitaxial growth of complex multilayers on Si has been explored-but besides complexity, high defect densities and junction leakage currents present limitations in this approach. Motivated by this challenge, here we use an epitaxial transfer method for the integration of ultrathin layers of single-crystal InAs on Si/SiO(2) substrates. As a parallel with silicon-on-insulator (SOI) technology, we use 'XOI' to represent our compound semiconductor-on-insulator platform. Through experiments and simulation, the electrical properties of InAs XOI transistors are explored, elucidating the critical role of quantum confinement in the transport properties of ultrathin XOI layers. Importantly, a high-quality InAs/dielectric interface is obtained by the use of a novel thermally grown interfacial InAsO(x) layer (~1 nm thick). The fabricated field-effect transistors exhibit a peak transconductance of ~1.6 mS µm(-1) at a drain-source voltage of 0.5 V, with an on/off current ratio of greater than 10,000.

Voltage-controlled ferroelastic switching in Pb(Zr0.2Ti0.8)O3 thin films.

We report a voltage controlled reversible creation and annihilation of a-axis oriented ∼10 nm wide ferroelastic nanodomains without a concurrent ferroelectric 180° switching of the surrounding c-domain matrix in archetypal ferroelectric Pb(Zr0.2Ti0.8)O3 thin films by using the piezo-response force microscopy technique. In previous studies, the coupled nature of ferroelectric switching and ferroelastic rotation has made it difficult to differentiate the underlying physics of ferroelastic domain wall movement. Our observation of distinct thresholds for ferroelectric and ferroelastic switching allows us investigate the ferroelastic switching cleanly and demonstrate a new degree of nanoscale control over the ferroelastic domains.

Room-temperature negative capacitance in a ferroelectric-dielectric superlattice heterostructure.

We demonstrate room-temperature negative capacitance in a ferroelectric-dielectric superlattice heterostructure. In epitaxially grown superlattice of ferroelectric BSTO (Ba0.8Sr0.2TiO3) and dielectric LAO (LaAlO3), capacitance was found to be larger compared to the constituent LAO (dielectric) capacitance. This enhancement of capacitance in a series combination of two capacitors indicates that the ferroelectric was stabilized in a state of negative capacitance. Negative capacitance was observed for superlattices grown on three different substrates (SrTiO3 (001), DyScO3 (110), and GdScO3 (110)) covering a large range of substrate strain. This demonstrates the robustness of the effect as well as potential for controlling the negative capacitance effect using epitaxial strain. Room-temperature demonstration of negative capacitance is an important step toward lowering the subthreshold swing in a transistor below the intrinsic thermodynamic limit of 60 mV/decade and thereby improving energy efficiency.

Real-time observation of local strain effects on nonvolatile ferroelectric memory storage mechanisms.

We use in situ transmission electron microscopy to directly observe, at high temporal and spatial resolution, the interaction of ferroelectric domains and dislocation networks within BiFeO3 thin films. The experimental observations are compared with a phase field model constructed to simulate the dynamics of domains in the presence of dislocations and their resulting strain fields. We demonstrate that a global network of misfit dislocations at the film-substrate interface can act as nucleation sites and slow down domain propagation in the vicinity of the dislocations. Networks of individual threading dislocations emanating from the film-electrode interface play a more dramatic role in pinning domain motion. These dislocations may be responsible for the domain behavior in ferroelectric thin-film devices deviating from conventional Kolmogorov-Avrami-Ishibashi dynamics toward a Nucleation Limited Switching model.

Non-volatile magnon transport in a single domain multiferroic.

Antiferromagnets have attracted significant attention in the field of magnonics, as promising candidates for ultralow-energy carriers for information transfer for future computing. The role of crystalline orientation distribution on magnon transport has received very little attention. In multiferroics such as BiFeO3 the coupling between antiferromagnetic and polar order imposes yet another boundary condition on spin transport. Thus, understanding the fundamentals of spin transport in such systems requires a single domain, a single crystal. We show that through Lanthanum (La) substitution, a single ferroelectric domain can be engineered with a stable, single-variant spin cycloid, controllable by an electric field. The spin transport in such a single domain displays a strong anisotropy, arising from the underlying spin cycloid lattice. Our work shows a pathway to understanding the fundamental origins of magnon transport in such a single domain multiferroic.

Dense electron system from gate-controlled surface metal-insulator transition.

Two-dimensional electron systems offer enormous opportunities for science discoveries and technological innovations. Here we report a dense electron system on the surface of single-crystal vanadium dioxide nanobeam via electrolyte gating. The overall conductance of the nanobeam increases by nearly 100 times at a gate voltage of 3 V. A series of experiments were carried out which rule out electrochemical reaction, impurity doping, and oxygen vacancy diffusion as the dominant mechanism for the conductance modulation. A surface insulator-to-metal transition is electrostatically triggered, thereby collapsing the bandgap and unleashing an extremely high density of free electrons from the original valence band within a depth self-limited by the energetics of the system. The dense surface electron system can be reversibly tuned by the gating electric field, which provides direct evidence of the electron correlation driving mechanism of the phase transition in VO(2). It also offers a new material platform for implementing Mott transistor and novel sensors and investigating low-dimensional correlated electron behavior.

How good can monolayer MoS2 transistors be?

Monolayer molybdenum disulfide (MoS(2)), unlike its bulk form, is a direct band gap semiconductor with a band gap of 1.8 eV. Recently, field-effect transistors have been demonstrated experimentally using a mechanically exfoliated MoS(2) monolayer, showing promising potential for next generation electronics. Here we project the ultimate performance limit of MoS(2) transistors by using nonequilibrium Green's function based quantum transport simulations. Our simulation results show that the strength of MoS(2) transistors lies in large ON-OFF current ratio (>10(10)), immunity to short channel effects (drain-induced barrier lowering ∼10 mV/V), and abrupt switching (subthreshold swing as low as 60 mV/decade). Our comparison of monolayer MoS(2) transistors to the state-of-the-art III-V materials based transistors, reveals that while MoS(2) transistors may not be ideal for high-performance applications due to heavier electron effective mass (m = 0.45 m(0)) and a lower mobility, they can be an attractive alternative for low power applications thanks to the large band gap and the excellent electrostatic integrity inherent in a two-dimensional system.