Doping Trends in HfOx Rram

Zinc oxide (ZnO) is an amorphous oxide semiconductor (AOS) material valued for its high carrier mobility, transparency to visible light, and low-temperature manufacturing process compared to silicon-based semiconductors. These desired features make ZnO-based AOSs widely popular as the channel layer in TFTs and as key dielectric layers in electronic devices like light sensors, gas detectors, resistive random-access memory (RRAM), and more. Among them, Conductive Bridge Random Access Memory (CBRAM) with a dielectric switching layer sandwiched between the electrochemically active metal (Ag, Cu) top electrode and the inert bottom electrode, is of a class of RRAM that offers low-voltage operation, high-density storage device, non-volatile, and compatibility with standard CMOS processes [1]. The CBRAM operates based on the principle of conductive filament formation and rupture. During operation, conductive filaments will be formed in switching layer by connecting metal ions which diffuse from the electrode after applying a positive bias. The device will switch to a low resistance state (LRS) after the conductive filaments were formed. After this, applying a negative bias will break the conductive filaments and switch the device back to a high resistance state (HRS). The HRS and LRS are the 0 or1 state of the memory operation. Studies and works have shown that controlling the distribution and diffusion of electrode metal ions in the switching layer is challenging because the conductive filaments formed can vary significantly in strength, ranging from robust to fragile [2]. This leads to instability in the operation of memory devices and encountering difficulties in the integration with TFT pixel array for memory-in-pixel (MiP) power-saving displays [3] or CMOS-integrated compute-in-memory applications [4].In this work, we proposed a novel CBRAM device featuring ZnO nanostructures as the resistive switching layer. The combination of a sputter-deposited seed layer with the water bath method enables the production of high-quality ZnO nanostructures at temperatures below 90°C. These nanostructures play a crucial role in constraining metal ion diffusion and filament formation, leading to the formation of uniform conductive filaments. This improvement significantly enhances the operational stability of the CBRAM device. The experimental results have demonstrated superior memory characteristics with a highly uniform distribution achieved successfully in the ZnO nanostructure-embedded CBRAM, compared to its counterpart lacking ZnO nanostructures. Furthermore, post-treatments are implemented in this study to further promote electrical performance of the nanostructure-embedded CBRAM, like operation voltage, memory window, retention, and endurance. Reference: [1] C. Gopalan, Y. Ma, T. Gallo, J. Wang, E. Runnion, J. Saenz, F. Koushan, P. Blanchard, S. Hollmer, “Demonstration of Conductive Bridging Random Access Memory (CBRAM) in logic CMOS process”, Solid-State Electronics, vol. 58 (1), p. 54-61, 2011.[2] C. C. Hsu, P. T. Liu, K. J. Gan, D. B. Ruan, Simon M. Sze, “Investigation of deposition technique and thickness effect of HfO2 film in bilayer InWZnO-based conductive bridge random access memory”, Vacuum, vol. 201, 111123, 2022.[3] S. H. Lee, B. C. Yu, H. J. Chung, and S. W. Lee, “Memory-in-pixel circuit for low-power liquid crystal displays comprising oxide thin-filmtransistors,” IEEE Electron Device Lett., vol. 11 (11), pp. 1551–1554, 2017.[4] W. Wan, R. Kubendran, C. Schaefer, et al., “A compute-in-memory chip based on resistive random-access memory”, Nature, vol. 608, p. 504–512, 2022.

Conductive-bridging random access memory (CBRAM) using a cobalt (Co) electrode has recently featured a CMOS-compatible process, excellent data retention, and a sub-μA operating current level, which are difficult to achieve by conventional CBRAM. However, the resistive switching (RS) mechanism of Co CBRAM has not been extensively explored compared to that of the conventional CBRAM cells using Ag, Cu, or Ni as active metal electrodes. Because only implicit inferences based on electrical measurements have been made, the formation of Co filaments is not yet clearly understood. This study presents evidence of Co filament formation in Co/10 nm SiOx/TiN resistive random access memory (RRAM) using direct transmission electron microscopy (TEM) observations. Co protrusions larger than 5 nm are observed, and their exact atomic composition is investigated by spectroscopy. We explain the RS operation of Co/SiOx/TiN cells based on the Co electromigration-mediated filament development process through Co electrode deformation, protrusion, and subsequent Co conductive bridge formation. An asymmetric RS operation and negative temperature correlation of the resistance are found in low resistance state (LRS) cells, which further supports the Co-involved RS operation in Co/SiOx/TiN devices.

Ferromagnetic conductive filaments (CFs) were formed in a conductive-bridge random access memory (CBRAM) with a Ni electrode using high current compliances during a set process. We investigated CFs in a Ni/HfO2/Pt CBRAM using the current compliance dependences of the set process, low-temperature characteristics, and anisotropic magnetoresistance (AMR). Set processes occurred when a positive bias was applied to the Ni electrode only; therefore, the switching phenomena showed polarity. The resistance of the ON state (low resistance state) was dependent on the current compliance between 2 and 5 mA. The ON state of the device showed a metallic conduction property, suggested by the temperature dependence of resistance. When a high current compliance (5 mA) was used for programming, the ON state showed AMR, which was direct evidence of ferromagnetic CF formation. This suggests that the formation of a ferromagnetic CF is associated with the accumulation of Ni ions that diffused from the Ni electrode. The OFF-state (high resistance state) resistance slightly increased with decreasing temperature and AMR was not observed.

The impact of TiW barrier layer thickness dependent transition from electro-chemical metallization memory to valence change memory in ZrO2-based resistive switching random access memory devices

The variation of resistive switching (RS) parameters is one of the major challenges to push resistive random access memory (RRAM) into application. In this paper, with a statistical methodology, for the first time we study the statistical distributions of set parameters of the Cu/HfO <inf xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</inf> /Pt based conductive bridge random access memory (CBRAM). The distributions of the set parameters in each off resistance range are shown to nicely fit a Weibull model. The Weibull slope and scale factor of the set voltage increase logarithmically with the geometric mean of off resistance in different ranges, which can be well explained by the cell-based percolation model of set statistics. And also for the first time, we revel that the Weibull slope of the set current decreases logarithmically with the off resistance. Our study is of significance to reduce the fluctuation of the resistive switching parameters.

In this paper, we investigate the quantized conduction behavior of conductive bridge random access memory (CBRAM) with varied materials and ramping rates. We report stable and reproducible quantized conductance states with integer multiples of fundamental conductance obtained by optimizing the voltage ramping rate and the Ti-diffusion barrier (DB) at the Cu/HfO2 interface. Owing to controlled diffusion of Cu ions by the Ti-DB and the optimized ramping rate, through which it was possible to control the time delay of Cu ion reduction, more than seven levels of discrete conductance states were clearly observed. Analytical modeling was performed to determine the rate-limiting step in filament growth based on an electrochemical redox reaction. Our understanding of the fundamental mechanisms of quantized conductance behaviors provide a promising future for the multi-bit CBRAM device.

Large parameter variability is identified as one of the main problems in conductive bridging random access memory (CBRAM) at the device level impeding large-scale commercial applications. Here, we ...

Here, we present the synaptic characteristics of AlN-based conductive bridge random access memory (CBRAM) as a synaptic device for neuromorphic systems. Both non-volatile and volatile memory are observed by simply controlling the strength of the Cu filament inside the AlN film. For non-volatile switching induced by high compliance current (CC), good retention with a strong Cu metallic filament is verified. Low-resistance state (LRS) and high-resistance state (HRS) conduction follow metallic Ohmic and trap-assisted tunneling (TAT), respectively, which are supported by I–V fitting and temperature dependence. The transition from long-term plasticity (LTP) to short-term plasticity (STP) is demonstrated by increasing the pulse interval time for synaptic device application. Also, paired-pulse facilitation (PPF) in the nervous system is mimicked by sending two identical pulses to the CBRAM device to induce STP. Finally, potentiation and depression are achieved by gradually increasing the set and reset voltage in pulse transient mode.

Uniformity and retention are crucial aspects for application of conductive bridge random access memory. In this letter, a self-aligned CuSiN interfacial layer was inserted into Cu/TaO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">x</sub> /Ru device to obtain a Cu/CuSiN/ TaO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">x</sub> /Ru structure. Compared with the Cu/TaO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">x</sub> /Ru device, the Cu/CuSiN/TaO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">x</sub> /Ru device shows much improved uniformity of resistance and programming voltage. Higher ON/ OFF ratio of <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$1000\times $ </tex-math></inline-formula> was observed, benefiting from the tight distribution of resistance. The standard deviation of set voltage was minimized from 0.635 to 0.187. Moreover, the low-resistance-state retention was also greatly improved. The uniformity and retention improvement could be well explained by the good controlment of cation injection and localization induced by CuSiN interfacial layer.

Control of filament growth within conductive bridge random access memories (CBRAM) is of crucial interest in order to ensure the reliability of such emerging devices. Here, we demonstrate that Scanning Joule Expansion Microscopy (SJEM) can be used to detect and precisely localize conductive filaments within operating crossbar CBRAM devices. Flexible memory devices based on Pd/Al2O3/Ag stacks are first elaborated at low temperature on polyimide substrate. These devices show set and reset operations at low voltage ( $4.3~\mu \text{m}$ is extracted at 50kHz and it is also demonstrated that the thermal expansion signal is proportional to the dissipated Joule power. We believe that the proposed procedure opens the way to reliability studies that can be applied to any family of memory device based on filamentary conduction.

The threshold switching effect is considered of outmost importance for a variety of applications ranging from the reliable operation of crossbar architectures to emulating neuromorphic properties with artificial neural networks. This property is strongly believed to be associated with the rich inherit dynamics of a metallic conductive filament (CF) formation and its respective relaxation processes. Understanding the origin of these dynamics is very important in order to control the degree of volatility and design novel electronic devices. Here, we present a synergistic numerical and experimental approach in order to deal with that issue. The distribution of relaxation time is addressed through time-resolved pulse measurements whereas the entire switching behavior is modeled through a 2D dynamical model by taking into account the destructive interference of the drift/diffusion transport mechanisms and the Soret diffusion flux due to the intense local Joule heating. The proposed mechanism interprets successfully both the threshold to bipolar switching transition as well as the self-rectifying effects in SiO2-based memories. The model incorporates the effect of electrode materials on the switching pattern and provides a different perception of the ionic transport processes, shading light into the ultra-small lifetimes of the CF and explaining the different behavior of the silver or copper active materials in a conductive bridge random access memory architecture.

The electrochemical metallization cell, also referred to as conductive bridge random access memory, is considered to be a promising candidate or complementary component to the traditional charge based memory. As such, it is receiving additional focus to accelerate the commercialization process. To create a successful mass product, reliability issues must first be rigorously solved. In-depth understanding of the failure behavior of the ECM is essential for performance optimization. Here, we reveal the degradation of high resistance state behaves as the majority cases of the endurance failure of the HfO2 electrolyte based ECM cell. High resolution transmission electron microscopy was used to characterize the change in filament nature after repetitive switching cycles. The result showed that Cu accumulation inside the filament played a dominant role in switching failure, which was further supported by measuring the retention of cycle dependent high resistance state and low resistance state. The clarified physical picture of filament evolution provides a basic understanding of the mechanisms of endurance and retention failure, and the relationship between them. Based on these results, applicable approaches for performance optimization can be implicatively developed, ranging from material tailoring to structure engineering and algorithm design.

The filament operation of resistive random-access memory was studied via in-situ transmission electron microscopy, and the contribution of the conductive filament to the resistance switching was experimentally confirmed. In addition to the operation principles, the device degradation mechanism was studied through repeated write/erase operations. The importance of controlling Cu movement in the switching layer was confirmed for stable CBRAM (conductive bridge random access memory) operations. A device structure with double switching layers and device miniaturization was effective in restricting over accumulation of Cu in the switching layer and localizing the filament. This may improve the robustness of the device against performance degradation.

Resistive switching mechanism of zirconium oxide-based resistive random access memory (RRAM) devices composed of Cu-doped ZrO2 film sandwiched between an oxidizable electrode and an inert electrode was investigated. The Ag/ZrO2:Cu/Pt RRAM devices with crosspoint structure fabricated by e-beam evaporation and e-beam lithography show reproducible bipolar resistive switching. The linear I–V relationship of low resistance state (LRS) and the dependence of LRS resistance (RON) and reset current (Ireset) on the set current compliance (Icomp) indicate that the observed resistive switching characteristics of the Ag/ZrO2:Cu/Pt device should be ascribed to the formation and annihilation of localized conductive filaments (CFs). The physical origin of CF was further analyzed by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS). CFs were directly observed by cross-sectional TEM. According to EDS and elemental mapping analysis, the main chemical composition of CF is determined by Ag atoms, coming from the Ag top electrode. On the basis of these experiments, we propose that the set and reset process of the device stem from the electrochemical reactions in the zirconium oxide under different external electrical stimuli.

The morphological evolution of the conducting filament (CF) predominantly controls the electric response of the resistive random access memory (ReRAM) devices. However, the parameters—in terms of the material and the processing—which control the growth of such CF are plenty. Extending the phase field technique for ReRAM systems presented by Roy and Cha [J. Appl. Phys. 128, 205102 (2020)], we could successfully model the complete SET (to attain low resistance state) and RESET (to attain high resistance state) processes due to the application of sweeping voltage. The key parameters that influence the stability of the multi-cycle I-V response or the endurance behavior are identified. The computational findings of the presented model ReRAM system are practical in correlating the multi-parametric influence with the stability, variability, and reliability of the endurance cycle that affect the device performance and also lead to the device failure. We believe that our computational approach of connecting the morphological changes of the CF with the electrical response has the potential to further understand and optimize the performance of the ReRAM devices.