Direct Assessment of Defective Regions in Monolayer MoS2 Field-Effect Transistors through In Situ Scanning Probe Microscopy Measurements.

Implementing two-dimensional materials in field-effect transistors (FETs) offers the opportunity to continue the scaling trend in the complementary metal-oxide-semiconductor technology roadmap. Presently, the search for electrically active defects, in terms of both their density of energy states and their spatial distribution, has turned out to be of paramount importance in synthetic transition metal dichalcogenides layers, as they are suspected of severely inhibiting these devices from achieving their highest performance. Although advanced microscopy tools have allowed the direct detection of physical defects such as grain boundaries and point defects, their implementation at the device scale to assess the active defect distribution and their impact on field-induced channel charge modulation and current transport is strictly restrained. Therefore, it becomes critical to directly probe the gate modulation effect on the carrier population at the nanoscale of an FET channel, with the objective to establish a direct correlation with the device characteristics. Here, we have investigated the active channel in a monolayer MoS2 FET through in situ scanning probe microscopy, namely, Kelvin probe force microscopy and scanning capacitance microscopy, to directly identify active defect sites and to improve our understanding of the contribution of grain boundaries, bilayer islands, and defective grain domains to channel conductance.

Significant Oxygen Underestimation When Quantifying Barium-Doped SrTiO Layers by Atom Probe Tomography.

In this paper, the capability for quantifying the composition of Ba-doped SrTiO layers from an atom probe measurement was explored. Rutherford backscattering spectrometry and time-of-flight/energy elastic recoil detection were used to benchmark the composition where the amount of titanium was intentionally varied between samples. The atom probe results showed a significant divergence from the benchmarked composition. The cause was shown to be a significant oxygen underestimation (≳14 at%). The ratio between oxygen and titanium for the samples varied between 2.6 and 12.7, while those measured by atom probe tomography were lower and covered a narrower range between 1.4 and 1.7. This difference was found to be associated with the oxygen and titanium predominantly field evaporating together as a molecular ion. The evaporation fields and bonding chemistries determined showed inconsistencies for explaining the oxygen underestimation and ion species measured. The measured ion charge state was in excellent agreement with that predicted by the Kingham postionization theory. Only by considering the measured ion species, their evaporation fields, the coordination chemistry, the analysis conditions, and some recently reported density functional theory modeling for oxide field emission were we able to postulate a field emission and oxygen neutral desorption process that may explain our results.

Standards for the Characterization of Endurance in Resistive Switching Devices.

Resistive switching (RS) devices are emerging electronic components that could have applications in multiple types of integrated circuits, including electronic memories, true random number generators, radiofrequency switches, neuromorphic vision sensors, and artificial neural networks. The main factor hindering the massive employment of RS devices in commercial circuits is related to variability and reliability issues, which are usually evaluated through switching endurance tests. However, we note that most studies that claimed high endurances >106 cycles were based on resistance versus cycle plots that contain very few data points (in many cases even <20), and which are collected in only one device. We recommend not to use such a characterization method because it is highly inaccurate and unreliable (i.e., it cannot reliably demonstrate that the device effectively switches in every cycle and it ignores cycle-to-cycle and device-to-device variability). This has created a blurry vision of the real performance of RS devices and in many cases has exaggerated their potential. This article proposes and describes a method for the correct characterization of switching endurance in RS devices; this method aims to construct endurance plots showing one data point per cycle and resistive state and combine data from multiple devices. Adopting this recommended method should result in more reliable literature in the field of RS technologies, which should accelerate their integration in commercial products.

Key material parameters driving CBRAM device performances.

This study is focused on Conductive Bridging Random Access Memory (CBRAM) devices based on chalcogenide electrolyte and Cu-supply materials, and aims at identifying the key material parameters controlling memory properties. The CBRAM devices investigated are integrated on CMOS select transistors, and are constituted by either Ge-Se or Ge-Te electrolyte layers of various compositions combined with a Cu2GeTe3 active chalcogenide electrode. By means of extensive physical and electrical characterization, we show for a given electrolyte system that slower write is obtained for a denser electrolyte layer, which is directly correlated with a lower atomic percentage of the chalcogen element in the layer. We also evidence that the use of Ge-Se electrolyte results in larger write energy (voltage and time), however with improved state retention properties than for Ge-Te electrolyte materials. We associate these results with the stronger chemical bonding of Cu with Se, resulting both in a stabilized Cu filament and a slower Cu cation motion. More robust processing thermal stability is also observed for Ge-Se compared to Ge-Te compounds, allowing more flexibility in the integration flow design.

Influence of the Chalcogen Element on the Filament Stability in CuIn(Te,Se,S)2/Al2O3 Filamentary Switching Devices.

In this paper, we report on the use of CuInX2 (X = Te, Se, S) as a cation supply layer in filamentary switching applications. Being used as absorber layers in solar cells, we take advantage of the reported Cu ionic conductivity of these materials to investigate the effect of the chalcogen element on filament stability. In situ X-ray diffraction showed material stability attractive for back-end-of-line in semiconductor industry. When integrated in 580 µm diameter memory cells, more volatile switching was found at low compliance current using CuInS2 and CuInSe2 compared to CuInTe2, which is ascribed to the natural tendency for Cu to diffuse back from the switching layer to the cation supply layer because of the larger difference in electrochemical potential using Se or S. Low-current and scaled behavior was also confirmed using conductive atomic force microscopy. Hence, by varying the chalcogen element, a method is presented to modulate the filament stability.

Direct Probing of the Dielectric Scavenging-Layer Interface in Oxide Filamentary-Based Valence Change Memory.

A great improvement in valence change memory performance has been recently achieved by adding another metallic layer to the simple metal-insulator-metal (MIM) structure. This metal layer is often referred to as oxygen exchange layer (OEL) and is introduced between one of the electrodes and the oxide. The OEL is believed to induce a distributed reservoir of defects at the metal-insulator interface thus providing an unlimited availability of building blocks for the conductive filament (CF). However, its role remains elusive and controversial owing to the difficulties to probe the interface between the OEL and the CF. Here, using Scalpel SPM we probe multiple functions of the OEL which have not yet been directly measured, for two popular VCMs material systems: Hf/HfO2 and Ta/Ta2O5. We locate and characterize in three-dimensions the volume containing the oxygen exchange layer and the CF with nanometer lateral resolution. We demonstrate that the OEL induces a thermodynamic barrier for the CF and estimate the minimum thickness of the OEL/oxide interface to guarantee the proper switching operations is ca. 3 nm. Our experimental observations are combined to first-principles thermodynamics and defect kinetics to elucidate the role of the OEL for device optimization.

Imaging the Three-Dimensional Conductive Channel in Filamentary-Based Oxide Resistive Switching Memory.

Filamentary-based oxide resistive memory is considered as a disruptive technology for nonvolatile data storage and reconfigurable logic. Currently accepted models explain the resistive switching in these devices through the presence/absence of a conductive filament (CF) that is described as a reversible nanosized valence-change in an oxide material. During device operation, the CF cycles billion of times at subnanosecond speed, using few tens of microamperes as operating current and thus determines the whole device's performance. Despite its importance, the CF observation is hampered by the small filament size and its minimal compositional difference with the surrounding material. Here we show an experimental solution to this problem and provide the three-dimensional (3D) characterization of the CF in a scaled device. For this purpose we have recently developed a tomography technique which combines the high spatial resolution of scanning probe microscopy with subnanometer precision in material removal, leading to a true 3D-probing metrology concept. We locate and characterize in three-dimensions the nanometric volume of the conductive filament in state-of-the-art bipolar oxide-based devices. Our measurements demonstrate that the switching occurs through the formation of a single conductive filament. The filaments exhibit sizes below 10 nm and present a constriction near the oxygen-inert electrode. Finally, different atomic-size contacts are observed as a function of the programming current, providing evidence for the filament's nature as a defects modulated quantum contact.

Understanding the Dual Nature of the Filament Dissolution in Conductive Bridging Devices.

The formation and rupture of conductive filaments (CFs) inside an insulating medium is used as hardware encoding of the state of a memory cell ("1" - "0") in filamentary-based conductive bridging memories. Currently accepted models explain the filament erase (reset) as the subtraction of conductive metal atoms from the CF; however, they do not fully account for the rich set of phenomena experimentally observed during the reset. The details of the filament erase are unraveled on the nanometer scale by means of an atomic force microscopy-based tomography technique enabling the 3D observation of erased CFs. "Non-broken" and "broken" CFs are observed, whereby the increase in resistance originates, respectively, from a constriction point in the current path and from an interrupted CF. We demonstrate that their existence and morphology can be related to the specific formation history of the CF, and we identify the physical volume of the CF as being mainly responsible for the type of filament erase.

Combinatorial Study of Ag-Te Thin Films and Their Application as Cation Supply Layer in CBRAM Cells.

In this work, we investigate binary Ag-Te thin films and their functionality as a cation supply layer in conductive bridge random access memory devices. A combinatorial sputter deposition technique is used to deposit a graded Ag(x)Te(1-x) (0 < x < 1) layer with varying composition as a function of the position on the substrate. The crystallinity, surface morphology, and material stability under thermal treatment as a function of the composition of the material are investigated. From this screening, a narrow composition range between 33 and 38 at% Te is selected which shows a good morphology and a high melting temperature. Functionality of a single Ag(2-δ)Te composition as cation supply layer in CBRAM with dedicated Al2O3 switching layer is then investigated by implementing it in 580 µm diameter dot Pt/Ag(2-δ)Te/Al2O3/Si cells. Switching properties are investigated and compared to cells with a pure Ag cation supply layer. An improved cycling behavior is observed when Te is added compared to pure Ag, which we relate to the ionic conducting properties of Ag2Te and the preferred formation of Ag-Te phases.

Three-dimensional observation of the conductive filament in nanoscaled resistive memory devices.

The basic unit of information in filamentary-based resistive switching memories is physically stored in a conductive filament. Therefore, the overall performance of the device is indissolubly related to the properties of such filament. In this Letter, we report for the first time on the three-dimensional (3D) observation of the shape of the conductive filament. The observation of the filament is done in a nanoscale conductive-bridging device, which is programmed under real operative conditions. To obtain the 3D-information we developed a dedicated tomography technique based on conductive atomic force microscopy. The shape and size of the conductive filament are obtained in three-dimensions with nanometric resolution. The observed filament presents a conical shape with the narrow part close to the inert-electrode. On the basis of this shape, we conclude that the dynamic filament-growth is limited by the cation transport. In addition, we demonstrate the role of the programming current, which clearly influences the physical-volume of the induced conductive filaments.

Switching mechanism and reverse engineering of low-power Cu-based resistive switching devices.

In the recent past, filamentary-based resistive switching devices have emerged as predominant candidates for future non-volatile memory storage. Most of the striking characteristics of these devices are still limited by the high power consumption and poor understanding of the intimate resistive switching mechanism. In this study, we present an atomic scale study of the filament formation in CuTe-Al2O3 by using a conductive scanning probe tip to analyse the shape and dimensions of the filament. Filaments studied were either created within a normal device or locally formed while using the tip as the top electrode. We demonstrate that it is possible to create with C-AFM a filament with a signature identical to a device (i.e. two orders of magnitude resistance window, 10(4) s retention operating at 5 µA). This is obtained by a dedicated material and resistance selection for the conductive tip. The filamentary mechanism of fully processed devices is demonstrated and observed by C-AFM. Filaments created with C-AFM can be repeatedly cycled and the ON state presents a 20 nm highly conductive spot which can be repeatedly turned into a poorly conductive path in the OFF state.

Influence of carbon alloying on the thermal stability and resistive switching behavior of copper-telluride based CBRAM cells.

We report the improved thermal stability of carbon alloyed Cu0.6Te0.4 for resistive memory applications. Copper-tellurium-based memory cells show enhanced switching behavior, but the complex sequence of phase transformations upon annealing is disadvantageous for integration in a device. We show that addition of about 40 at % carbon to the Cu-telluride layer results in an amorphous material up to 360 °C. This material was then integrated in a TiN/Cu0.6Te0.4-C/Al2O3/Si resistive memory cell, and compared to pure Cu0.6Te0.4. Very attractive endurance (up to 1 × 10(3) cycles) and retention properties (up to 1 × 10(4) s at 85 °C) are observed. The enhanced thermal stability and good switching behavior make this material a promising candidate for integration in memory devices.

Electrodeposition of copper tetracyanoquinodimethane for bipolar resistive switching non-volatile memories.

Electrodeposition experiments of the charge-transfer complex copper tetracyanoquinodimethane (CuTCNQ) (where TCNQ denotes 7,7',8,8'-tetracyanoquinodimethane) on noble metal electrodes (M=Pt and Au) were optimized in order to produce suitable layers for bipolar resistive switching cross-bar M/CuTCNQ/Al memory cells. Corresponding memories exhibited up to more than 10 000 consecutive write/erase cycles, with very stable on and off reading currents and an on/off current ratio of 10. CuTCNQ electrodeposition techniques were furthermore optimized for growing the material in 250 nm diameter contact holes of complementary metal oxide semiconductor dies with tungsten bottom contacts.