Nonvolatile Memory Applications Research Articles

Ferroelectric polarization and conductance filament coupling for large window and high-reliability resistive memory and energy-efficient synaptic devices

Ferroelectric capacitors hold great promise for non-volatile memory applications. However, the challenge lies in fabricating resistive switching devices with a high on/off ratio, excellent non-volatility, and a simple manufacturing process. Here, a novel approach is introduced by demonstrating the efficacy of the coupling effect between ferroelectric polarization and oxygen vacancy-based conductive filaments in Hf0.5Zr0.5O2 (HZO) films for the creation of non-volatile resistive switching memory devices, achieving an impressive on/off ratio of 6.8 × 103 at +1.8 V. An in-depth exploration of the resistive switching mechanism is provided and subsequently the outstanding durability and retention characteristics of these devices for resistive switching is validated. Furthermore, the device’s capacity to emulate non-volatile synaptic functionalities is assessed. Our results reveal that under pulsed conditions of 1 V/–2 V with 1 µs pulses spaced 50 ms apart, the device can robustly achieve potentiation/depression synaptic plasticity, while exhibiting energy consumption (0.16 fJ for potentiation, 0.12 fJ for depression) reduced by 1–2 orders of magnitude compared to biological synapses. This work holds significant value as a reference for the fabrication of energy-efficient, non-volatile memory and synaptic devices.

Bistable magnetic nanowires: A new approach to non-volatile memory with single readout and automatic deletion

A novel approach for a non-volatile destructive readout memory application using bistable magnetic nanowire arrays is presented. The encoded information is stored as binary 1 and 0 by groups of NWs magnetized in the positive and negative states, respectively. We leverage the naturally occurring switching field distribution of the NW array and a tailored alternating decreasing magnetic field to program remanent magnetic states. To retrieve the information, the measured remagnetization curve exhibits a star-like behavior with jumps and plateaus and its derivative converts this information to a binary-type format. Two encoding and readout schemes are proposed and validated: binary bits and barcodes. For each case, the implementation and optimization procedures are illustrated, along with the required processing to obtain a useful readout signal. This strategy holds potential for non-volatile memory applications in which the stored information is erased during reading and can be reused indefinitely.Graphical abstract

2D Ferroic Materials for Nonvolatile Memory Applications.

The emerging nonvolatile memory technologies based on ferroic materials are promising for producing high-speed, low-power, and high-density memory in the field ofintegrated circuits. Long-range ferroic orders observed in 2D materials have triggered extensive research interest in 2D magnets, 2D ferroelectrics, 2D multiferroics, and their device applications. Devices based on 2D ferroic materials and heterostructures with an atomically smooth interface and ultrathin thickness have exhibited impressive properties and significant potential for developing advanced nonvolatile memory. In this context, a systematic review of emergent 2D ferroic materials is conducted here, emphasizing their recent research on nonvolatile memory applications, with a view to proposing brighter prospects for 2D magnetic materials, 2D ferroelectric materials, 2D multiferroic materials, and their relevant devices.

Design and analysis of novel La:HfO2 gate stacked ferroelectric tunnel FET for non-volatile memory applications

Recent experimental studies have shown lanthanum-doped hafnium oxide (La:HfO2) possessing ferroelectric properties. This material is of special interest since it is based on lead-free, simple binary oxide of HfO2, and has excellent endurance property (1 × 109 field cycles without fatigue. There exists substantial information about the material aspects of La:HfO2 but it lacks proven application potential for CMOS-compatible low-power memory design. In this work, 10 % La metal cation fraction of HfO2 (La:HfO2) is proposed as the gate stack material in tunnel FET (TFET) for its potential as a memory device. 2D device simulations are carried out to show that the proposed ferroelectric TFET (FeTFET) provides the largest memory window (MW) as compared to present perovskite ferroelectric materials such as PZT, SBT (SrBi2Ta2O9) and silicon doped (4.6 % Si in HfO2) hafnium oxide (Si:HfO2). The larger window is attributed to greater polarization, and the calculation of MW is quantified by the shift in threshold voltage (Vth). The simulations carried out in this work suggest that La:HfO2 can be adopted as a potential ferroelectric material to target low-power FeTFET design at significantly reduced ferroelectric layer thickness.

Characterization of program and erase speed of memory capacitors with nanolaminated HfO2/Al2O3 stacks for application in non-volatile memories

The programming and erase performance of atomic layer deposited HfO2/Al2O3 memory stacks is investigated depending on the thickness of the tunnel oxide and the annealing of the structures. The as-grown stacks require applying of voltage pulses with duration of about 10-3 s for a measurable electron trapping (programming). The time dependence of the electron trapping process is quite sharp initially - the increase of the charging time from 4×10-4 s to 4×10-3 s provides more than 80% of the saturation value of the trapped charge obtained at durations above 1 s. The annealing increases the time needed for the onset of the electron trapping. For the chosen voltage amplitudes the programming characteristics does not depend on the tunnel oxide thickness. The electron detrapping (erase) is observed even at durations of ~10-7 s, but with a low efficiency. The erase characteristics is more gradual then the program one, and shows some dependence on tunnel oxide and annealing. The complete erase is achieved for times comparable to those for programming the cell. Erase pulses with duration > 10-2 s results to accumulation of positive charge in the capacitors.

Investigation of Resistive Switching of Insulating Hafnium Nitride for Nonvolatile Memory Applications

In this study, nitrogen-rich Hafnium Nitride (HfN) featuring insulating properties was investigated for achieving resistive switching, crucial for the functionality of resistive random-access memory (ReRAM) devices. Devices were fabricated with a 15-nm HfN resistive switching layer using a Radio Frequency (RF) sputtering system. The fabricated devices successfully exhibited a bipolar switching characteristic with a high On/Off ratio (up to 104). An interesting 2-step behavior was also observed during the formation of the conduction filament which was suspected to be tied to the migration of the nitrogen ions. This is the first attempt at using HfN as the resistive switching material for nonvolatile memory applications.

Realization of Selector‐Memory Bi‐Functionality with Self‐Current Regulation Utilizing Poly‐Crystalline Based GST Electrolyte for Memristor Hardware Development

AbstractConductive bridge random‐access memory (CBRAM) are two terminal devices that offer excellent switching performance. In addition, CBRAM shows various switching modes, including volatile threshold switching (TS) and nonvolatile threshold switching (N‐TS). These properties expand its applications to memory, selector, biological synapses, and neurons. However, due to the uncontrollable behavior of stochastic switching between TS and N‐TS in CBRAM devices, a novel approach is needed to improve the switching performance of CBRAM. Moreover, conventional devices that have different stacking between TS and N‐TS increase fabrication cost and worsen the device yield. Here, the selector‐memory bi‐functionality with self‐current regulation effect of Ag‐inserted Ge2Sb2Te5 (GST) thin films is demonstrated. Selector‐memory bi‐functionality, having TS behavior with an adjustable on/off current, with confined conductive filaments (CFs) improves the uniformity and reduces the fabrication cost by implementing TS/N‐TS in a single stack. From the material analysis, it becomes evident that confined Ag‐based CFs within GST films are key factors for realizing selector‐memory bi‐functionality. The selector‐memory bi‐functionality is achieved through the reaction of Ag metal cations with non‐bonded Te atoms in GST film depending on field polarity. These results suggest that the Ag‐inserted GST film contributes to the development of large‐scale nonvolatile memory and neuromorphic application.

Roadmap for ferroelectric domain wall memory

Commercial nonvolatile Ferroelectric Random Access Memory employs a destructive readout scheme based on charge sensing, which limits its cell scalability in sizes above 100 nm. Ferroelectric domain walls are two-dimensional topological interfaces with thicknesses approaching the unit cell level between two antiparallel domains and exhibit electrical conductivity, distinguishing them from insulating matrices that are uniformly ordered. Recently, novel research has been devoted to utilizing this extraordinary interface for the application in nonvolatile memory with nanometer-sized scalability and low energy consumption. Here, we pay more attention to the development of the domain wall memory technologies in the future with challenges and opportunities to design planar and vertical arrays of the memory cells in the CMOS platform.

Frequency-Dependent Multistep Ferroelectric Polarization Switching Mechanism in P(VDF-TrFE)-Based Capacitors Induced by Polystyrene Electret-like Modulation.

In this work, we investigate multistep ferroelectric polarization switching dynamics of a series of poly(vinylidene fluoride-trifluoroethylene)/polystyrene, P(VDF-TrFE)/PS, as active layers in ferroelectric capacitors with variable P(VDF-TrFE)/PS thickness ratios and a wide range of driving voltage frequencies (1-1000 Hz). The PS electret-like modulation effects on the depolarized field fluctuation are proven to be responsible for this multistep ferroelectric polarization switching process. To be specific, the switching current density peak splits into two peaks in both positive and negative voltage ranges according to the stimulus-response (S-R) data from the metal-ferroelectric-electret-metal capacitor driven by a periodic triangular voltage wave. The double-peak current trough appears when the transitorily suppressed ferroelectric polarization switching occurs while the discharge and recharge of the PS electret by external voltage brings a specific dynamic change in the electric field across ferroelectric (EFE). We also propose a theoretical model to simulate the ferroelectric polarization switching process at a current trough zone. This phenomenon provides new concepts on the electret-modulated multistep ferroelectric switching dynamics, and such switching mechanisms are critical for realizing reliable nonvolatile memory applications in flexible electronics.

Exploring non-stoichiometric SiOx thin film for non-volatile memory application

This article explores the electrical performance of capacitive memory and resistive switching (RS) devices based on thin films of a single active layer of Silicon oxide (SiOx). The fabricated device Au/SiOx/p-Si displayed frequency-dependent characteristics ranging from 200 kHz to 1 MHz w.r.t capacitance. The charge trapping nature was also investigated, which revealed a charge storage density (N) of order 1010 cm−2 and a low trapping density of interface (Dit) ∼2.65 × 1011 eV−1 cm−2. Furthermore, the device exhibits bipolar RS behavior while maintaining a stable endurance for 1000 DC sweeping cycles and a good retention period of > 103 s. The major pathway of the conduction mechanism in these devices is attributed to the accumulation of oxygen vacancies near the Au/SiOx interface. The conduction in this device is predominantly governed by trap-mediated space-charge-limited current (SCLC) and ohmic conductions.

Building a depletion-region width modulation model and realizing memory characteristics in PN heterostructure devices.

Memristive systems have potential applications in nonvolatile memories and even unexplored functionalities in electronics. However, progress has been delayed by difficulties in the controllability of memory behaviors and the dependence on material conductivity. Considering this, a new depletion-region width modulation model is proposed to realize and explain memory characteristics. The coexistence of memristive and memcapacitive behaviors is demonstrated in p-CuAlO2/n-ZnO, p+-Si/n-ZnO and p-NiO/n-ZnO heterostructure devices. A high external electric field induces the migration of oxygen ions and electrons/holes between the p-type and n-type semiconductor layers. It can regulate the oxygen vacancy concentration of the n-type side and cation vacancy concentration of the p-type side, changing the depletion-region width and modulating device conductivity and capacitance. Several essential synaptic functions were accurately imitated, including spike-timing-dependent plasticity (STDP) and "learning-experience" behaviors. This work provides new opportunities in fabricating a memristor and memcapacitor based on a PN heterostructure for synaptic simulation.

CuInS2 quantum dots-based unipolar resistive switching for non-volatile memory applications.

Recent advancements have established quantum dots (QDs) as a promising alternative to conventional bulk materials in the fabrication of nanoscale integrated electronic devices. The appeal of QDs lies in their amenability to low-temperature processes and solution-based methodologies, facilitating the construction of devices with enhanced versatility and efficiency. The ternary metal chalcogenide CuInS2 QDs are one of the foremost, eco-friendly, and highly stable materials. In this study, CuInS2 QDs are employed as a functional layer in a memristive device featuring an Al/CuInS2/ITO configuration. The CuInS2 QDs have been synthesized by a hot injection method and characterized using X-ray diffraction (XRD) and transmission electron microscopy (TEM) to reveal their structural features. The Al/CuInS2/ITO device shows a unipolar resistive switching (RS) behaviour with a high on/off ratio of 105. The switching parameters have been studied for 100 cycles of SET/RESET. The SET and RESET voltages are found to be 1.66 ± 0.25 V and 0.69 ± 0.17 V. The spatial variability of switching parameters in the Al/CuInS2/ITO structure has also been studied for 9 different devices. The device also exhibits unipolar RS behaviour in the optimum temperature range of 0 °C to 50 °C. These outcomes demonstrate the impressive performance of CuInS2 QDs, indicating their potential for future energy-efficient and large-scale non-volatile memory applications.

In situ atomic-scale observation of transformation from disordered to ordered layered structures in Ge-Sb-Te phase change memory thin films

Ge-Sb-Te (GST) thin films are emerging materials for various non-volatile memory applications. The compounds contain a huge number of vacancies that play important roles in structural and electronic transitions. Control of disorder and understanding the structural transformations in GST thin films are of great importance for the design and reliability of phase change memory devices. In this work, in situ heating atomic-resolution transmission electron microscopy is used to observe structural transformations from vacancy disordered (fcc) to layered ordered (vacancy-ordered (vo)) and van der Waals-bonded trigonal (vdW t)) structures. Starting from 160 °C, randomly distributed vacancies in fcc grains gradually accumulate into vacancy layers. Further heating to 220 and 240 °C results in the formation of vdW t-domains within the vo-GST grains and the formation of large <001>-oriented t-grains, in a good agreement with outcomes on in situ XRD heating of epitaxial vo-GST thin film. Moreover, vo and fcc GST structures can coexist with vdW t-structure in one grain. Full transformation to 〈112¯0〉-oriented t-grains occurs at 280 °C. Unlike other grains, the 〈001〉 t-grains show abnormal grain growth behaviour, while the electron beam irradiation accelerates the growth. Detailed characterizations of vo-grains reveal transient structures that indicate shear transformation mechanism and different defects as well as chemical changes during the transformations. Overall, this study provides new insights to understand the phase transition mechanisms and to optimize the microstructure in thin GST layers.

Tunable multiple nonvolatile resistance states in a MnSe-based van der Waals multiferroic tunnel junction.

Two-dimensional (2D) van der Waals (vdW) multiferroic tunnel junctions (MFTJs) composed of a ferromagnetic metal and a ferroelectric barrier have controllable thickness and clean interface and can realize the coexistence of tunneling magnetoresistance (TMR) and tunneling electroresistance (TER). Therefore, they have enormous potential application in nonvolatile multistate memories. Here, using first principles combined with non-equilibrium Green's function method, we have systematically investigated the spin-dependent transport properties of Fe3GeTe2/MnSe/Fe3GeTe2 vdW MFTJs with various numbers of barrier layers. By controlling the polarization orientation of the ferroelectric barrier MnSe and the magnetization alignment of the ferromagnetic electrodes Fe3GeTe2, the MnSe-based MFTJs exhibit four nonvolatile resistance states, with the TMR (TER) becoming higher and reaching a maximum of 1.4 × 106% (4114%) as the MnSe layers increase from a bilayer to a tetralayer. Using asymmetric Cu and Fe3GeTe2 as the electrodes, the TER can be further improved from 349% to 618%. Moreover, there is a perfect spin filtering effect in these MFTJs. This work demonstrates the potential applications of MnSe-based devices in multistate nonvolatile memories and spin filters, which will stimulate experimental studies on layer-controllable spintronic devices.

A floating-gate field-effect transistor memory device based on organic crystals with a built-in tunneling dielectric by a one-step growth strategy.

A floating-gate organic field-effect transistor (FG-OFET) memory device is becoming a promising candidate for emerging non-volatile memory applications due to the advantages of its sophisticated data-storage mechanism and reliable long-term data retention capacity. However, a conventional FG-OFET memory device suffers from complex fabrication technologies and poor mechanical flexibility, which limits its practical applications. Here, we propose a facile one-step liquid-surface drag coating strategy to fabricate a layered stack of 2,8-difluoro-5,11-bis(triethylsilylethynyl) anthradithiophene (Dif-TES-ADT) crystals and high-quality insulating polymer polystyrene (PS). The liquid surface enhances the spreading area of an organic solution and facilitates the unidirectional growth of organic crystals. In the bilayer-structured blend, the bottom PS polymer and the top Dif-TES-ADT semiconductor serve as a tunneling dielectric and an active memory layer of an FG-OFET memory device, respectively. Consequently, a flexible FG-OFET memory device with a large memory window of 41.4 V, a long retention time of 5000 s, and a high current ON/OFF ratio of 105 could be achieved, showing the best performance ever reported for organic thin film-based FG-OFET memory devices. In addition, multi-level data storage (3 bits per cell) can be achieved by tuning the gate voltage magnitude. Our work not only provides a general strategy for the growth of high-quality organic crystals, but also paves the way towards high-performance flexible memory devices.

A carbonyl-decorated two-dimensional polymer as a charge-trapping layer for non-volatile memory storage devices with a high endurance and wide memory window.

The charge-trapping mechanism in conjugated polymers is a performance obstacle in many optoelectronic devices harnessed for non-volatile memory applications. Herein, a carbonyl-decorated organic 2D-polymer (TpDb)-based charge-trapping memory device has been developed with a wide memory window (3.2 V) with low programming and erasing voltages of +3/-2 and -3/+2. The TpDb was synthesized by a potentially scalable solid-state aldol condensation reaction. The inherent structural defects and the semi-conjugated nature of the enone network in TpDb offer effective charge-trapping through the localization of charges in specific functional groups (CO). The interlayer hydrogen bonding enhances the packing density of the 2D-polymer layers thereby improving the memory storage properties of the material. Furthermore, the TpDb exhibits excellent features for non-volatile memory applications including over 10 000 cycles of write/read endurance and a prolonged retention performance of 104 seconds at high temperatures (100 °C).

In-Situ Reflectance Absorption Infra-Red Spectroscopy (RAIRS) Study on ALD of HfO2 on TiN and Pt Electrodes

Ferroelectricity in hafnia fluoride analogues has been widely investigated for nonvolatile memory applications. Although ALD of HfO2 technology is enough mature for CMOS technology, hafnia-based ferroelectrics still suffer from major reliability issues such as relaxation, imprint, fatigue, and breakdown.1 These reliability characteristics are thought to be related to the interface conditions between the ferroelectric film and the electrode. Thus, many reports suggested routes to enhance reliability and ferroelectric characteristics by modifying the interface states of the metal-ferroelectric-metal (MFM) capacitors. Unfortunately, only few reports disclose direct observation on evolution of interface formation and its mechanism. Recently, it is reported that scaling down the ferroelectric hafnia-based films to a few nm range dramatically improves the MFM capacitors’ reliability where the series capacitance and surface effect dominate, making it crucial to understand the interface properties carefully.2 In this presentation, we perform In-situ characterization using reflectance absorption infrared spectroscopy (RAIRS) to monitor the surface reaction and interface formation while HfOx ALD using TDMA-Hf with various oxidation reactants, such as H2O, O3, and anhydrous H2O2. TiN and Pt bottom electrodes are investigated at 250 °C. The RAIRS results show that the initial exposure of the oxidant generates the most amount of oxidation on the TiN surface by showing Ti-O and TiN-O peaks which were not observed for the Pt substrate. Moreover, the Ti-O and TiN-O peak area increase versus the dosing time of oxidant was minimum for H2O, and O3 showed continuous peak increase even after 12 s exposure. Interestingly, for the H2O2 case, there was almost no peak increase in the Ti-O bond region like H2O, but the TiN-O and TiO-O peaks appeared after the first 3 s and saturated after 6 s exposure. Also, not only on the TiN substrate, the peak for O-O stretching was observed for the Pt substrate as well, indicating that the H2O2 generates self-limiting peroxide bonds on the surface with a minimum interface formation. This suppressed interface formation with superior film properties using H2O2 might be the reason behind the robust reliability of the H2O2-based HZO capacitor. We are going to report reliability characteristics in conjunction with interface evolution.Acknowledements: We thank to YEST and KEIT for supporting the project through ISTD Program (No.20010806). This work is also supported by GRC-LMD program (task#3001.001) through SRC. The BRUTE hydrogen peroxide was provided by RASIRC. Ozone generator for TMEICReferences 1 J. Mohan et al., ACS AELM, 4, 4 (2022). 2 K. Toprasertpong et al., ACS AMI, 14 (2022).

Nonvolatile Memristive Effect in Few-Layer CrI3 Driven by Electrostatic Gating.

The potential of memristive devices for applications in nonvolatile memory and neuromorphic computing has sparked considerable interest, particularly in exploring memristive effects in two-dimensional (2D) magnetic materials. However, the progress in developing nonvolatile, magnetic field-free memristive devices using 2D magnets has been limited. In this work, we report an electrostatic-gating-induced nonvolatile memristive effect in CrI3-based tunnel junctions. The few-layer CrI3-based tunnel junction manifests notable hysteresis in its tunneling resistance as a function of gate voltage. We further engineered a nonvolatile memristor using the CrI3 tunneling junction with low writing power and at zero magnetic field. We show that the hysteretic transport observed is not a result of trivial effects or inherent magnetic properties of CrI3. We propose a potential association between the memristive effect and the newly predicted ferroelectricity in CrI3 via gating-induced Jahn-Teller distortion. Our work illuminates the potential of 2D magnets in developing next-generation advanced computing technologies.

First-principles prediction of two-dimensional Rare-earth intrinsic ferrovalley materials: Non-Janus GdXY (X≠Y=Cl,Br,I) monolayers

Two-dimensional ferrovalley magnetic materials have attracted much attention due to the applications in valley-based nonvolatile random access memories and valley filters. In this work, using first-principles calculations, we predict a promising class of bipolar magnetic semiconductors, namely non-Janus GdXY(X≠Y=Cl,Br,I) monolayers, which exhibit excellent mechanical and thermal stability, large magnetic moment (8 μB/Gd), and high Curie temperature (above 450 K). When magnetized along the ±z direction, a spontaneous valley polarization can be observed in non-Janus GdXY. Due to the non-zero Berry curvature, the anomalous Hall effect will be able to be observed in non-Janus GdXY. In addition, the system transforms into a semi-semiconductor from a bipolar magnetic semiconductor with increasing biaxial tensile strain. Under the strain of -4%∼+4%, the ferrovalley characteristics can be well maintained. Our findings not only reveal that non-Janus GdXY is a novel room-temperature ferrovalley semiconductor material, but also provide a new platform for designing spintronics and valley electronics devices.

The strain-induced transitions of the piezoelectric, pyroelectric, and electrocaloric properties of the CuInP2S6 films

Low-dimensional ferroelectrics, ferrielectrics, and antiferroelectrics are of urgent scientific interest due to their unusual polar, piezoelectric, electrocaloric, and pyroelectric properties. The strain engineering and strain control of the ferroelectric properties of layered two-dimensional van der Waals materials, such as CuInP2(S,Se)6 monolayers, thin films, and nanoflakes, are of fundamental interest and especially promising for their advanced applications in nanoscale nonvolatile memories, energy conversion and storage, nano-coolers, and sensors. Here, we study the polar, piezoelectric, electrocaloric, and pyroelectric properties of thin strained films of a ferrielectric CuInP2S6 covered by semiconducting electrodes and reveal an unusually strong effect of a mismatch strain on these properties. In particular, the sign of the mismatch strain and its magnitude determine the complicated behavior of piezoelectric, electrocaloric, and pyroelectric responses. The strain effect on these properties is opposite, i.e., “anomalous,” in comparison with many other ferroelectric films, for which the out-of-plane remanent polarization, piezoelectric, electrocaloric, and pyroelectric responses increase strongly for tensile strains and decrease or vanish for compressive strains.