Application of phase-change materials in memory taxonomy

Abstract

Phase-change materials are suitable for data storage because they exhibit reversible transitions between crystalline and amorphous states that have distinguishable electrical and optical properties. Consequently, these materials find applications in diverse memory devices ranging from conventional optical discs to emerging nanophotonic devices. Current research efforts are mostly devoted to phase-change random access memory, whereas the applications of phase-change materials in other types of memory devices are rarely reported. Here we review the physical principles of phase-change materials and devices aiming to help researchers understand the concept of phase-change memory. We classify phase-change memory devices into phase-change optical disc, phase-change scanning probe memory, phase-change random access memory, and phase-change nanophotonic device, according to their locations in memory hierarchy. For each device type we discuss the physical principles in conjunction with merits and weakness for data storage applications. We also outline state-of-the-art technologies and future prospects.     

Core-shell heterostructured phase change nanowire multistate memory

Phase-change memory, which switches reversibly between crystalline and amorphous phases, is promising for next generation data-storage devices. In this work, we present a novel, nonbinary data-storage device using core-shell nanowires to significantly enhance memory capacity by combining two phase-change materials with different electronic and thermal properties to engineer different onsets of amorphous-crystalline transitions. Electric-field induced sequential amorphous-crystalline transition in core-shell nanowires displays three distinct electronic states with high, low, and intermediate resistances, assigned as data "0", "1", and "2".     

Phase-change materials for rewriteable data storage

Phase-change materials are some of the most promising materials for data-storage applications. They are already used in rewriteable optical data storage and offer great potential as an emerging non-volatile electronic memory. This review looks at the unique property combination that characterizes phase-change materials. The crystalline state often shows an octahedral-like atomic arrangement, frequently accompanied by pronounced lattice distortions and huge vacancy concentrations. This can be attributed to the chemical bonding in phase-change alloys, which is promoted by p-orbitals. From this insight, phase-change alloys with desired properties can be designed. This is demonstrated for the optical properties of phase-change alloys, in particular the contrast between the amorphous and crystalline states. The origin of the fast crystallization kinetics is also discussed.     

Solution-phase deposition and nanopatterning of GeSbSe phase-change materials

Chalcogenide films with reversible amorphous-crystalline phase transitions have been commercialized as optically rewritable data-storage media, and intensive effort is now focused on integrating them into electrically addressed non-volatile memory devices (phase-change random-access memory or PCRAM). Although optical data storage is accomplished by laser-induced heating of continuous films, electronic memory requires integration of discrete nanoscale phase-change material features with read/write electronics. Currently, phase-change films are most commonly deposited by sputter deposition, and patterned by conventional lithography. Metal chalcogenide films for transistor applications have recently been deposited by a low-temperature, solution-phase route. Here, we extend this methodology to prepare thin films and nanostructures of GeSbSe phase-change materials. We report the ready tuneability of phase-change properties in GeSbSe films through composition variation achieved by combining novel precursors in solution. Rapid, submicrosecond phase switching is observed by laser-pulse annealing. We also demonstrate that prepatterned holes can be filled to fabricate phase-change nanostructures from hundreds down to tens of nanometres in size, offering enhanced flexibility in fabricating PCRAM devices with reduced current requirements.     

High-resolution transmission electron microscopy study of electrically-driven reversible phase change in ge2sb2te5 nanowires

By combining high-resolution transmission electron microscopy (HRTEM) characterization and electrical measurements on a unique device platform, we study the reversible electrically-driven phase-change characteristics of self-assembled Ge(2)Sb(2)Te(5) nanowires. Detailed HRTEM analyses are used to correlate and understand the effect of full and intermediate structural transformations on the measured electrical properties of the nanowire devices. The study demonstrates that our unique approach has the potential to provide new information regarding the dynamic structural and electrical states of phase-change materials at the nanoscale, which will aid the design of future phase-change memory devices.     

Interfacial phase-change memory

Phase-change memory technology relies on the electrical and optical properties of certain materials changing substantially when the atomic structure of the material is altered by heating or some other excitation process. For example, switching the composite Ge(2)Sb(2)Te(5) (GST) alloy from its covalently bonded amorphous phase to its resonantly bonded metastable cubic crystalline phase decreases the resistivity by three orders of magnitude, and also increases reflectivity across the visible spectrum. Moreover, phase-change memory based on GST is scalable, and is therefore a candidate to replace Flash memory for non-volatile data storage applications. The energy needed to switch between the two phases depends on the intrinsic properties of the phase-change material and the device architecture; this energy is usually supplied by laser or electrical pulses. The switching energy for GST can be reduced by limiting the movement of the atoms to a single dimension, thus substantially reducing the entropic losses associated with the phase-change process. In particular, aligning the c-axis of a hexagonal Sb(2)Te(3) layer and the 〈111〉 direction of a cubic GeTe layer in a superlattice structure creates a material in which Ge atoms can switch between octahedral sites and lower-coordination sites at the interface of the superlattice layers. Here we demonstrate GeTe/Sb(2)Te(3) interfacial phase-change memory (IPCM) data storage devices with reduced switching energies, improved write-erase cycle lifetimes and faster switching speeds.     

Ultra-high-density phase-change storage and memory

Phase-change storage is widely used in optical information technologies (DVD, CD-ROM and so on), and recently it has also been considered for non-volatile memory applications. This work reports advances in thermal data recording of phase-change materials. Specifically, we show erasable thermal phase-change recording at a storage density of 3.3 Tb inch(-2), which is three orders of magnitude denser than that currently achievable with commercial optical storage technologies. We demonstrate the concept of a thin-film nanoheater to realize ultra-small heat spots with dimensions of less than 50 nm. Finally, we show in a proof-of-concept demonstration that an individual thin-film heater can write, erase and read the phase of these storage materials at competitive speeds. This work provides important stepping stones for a very-high-density storage or memory technology based on phase-change materials.     

Nonvolatile Memories Based on Graphene and Related 2D Materials

The pervasiveness of information technologies is generating an impressive amount of data, which need to be accessed very quickly. Nonvolatile memories (NVMs) are making inroads into high‐capacity storage to replace hard disk drives, fuelling the expansion of the global storage memory market. As silicon‐based flash memories are approaching their fundamental limit, vertical stacking of multiple memory cell layers, innovative device concepts, and novel materials are being investigated. In this context, emerging 2D materials, such as graphene, transition metal dichalcogenides, and black phosphorous, offer a host of physical and chemical properties, which could both improve existing memory technologies and enable the next generation of low‐cost, flexible, and wearable storage devices. Herein, an overview of graphene and related 2D materials (GRMs) in different types of NVM cells is provided, including resistive random‐access, flash, magnetic and phase‐change memories. The physical and chemical mechanisms underlying the switching of GRM‐based memory devices studied in the last decade are discussed. Although at this stage most of the proof‐of‐concept devices investigated do not compete with state‐of‐the‐art devices, a number of promising technological advancements have emerged. Here, the most relevant material properties and device structures are analyzed, emphasizing opportunities and challenges toward the realization of practical NVM devices.     

Design rules for phase-change materials in data storage applications

Phase-change materials can rapidly and reversibly be switched between an amorphous and a crystalline phase. Since both phases are characterized by very different optical and electrical properties, these materials can be employed for rewritable optical and electrical data storage. Hence, there are considerable efforts to identify suitable materials, and to optimize them with respect to specific applications. Design rules that can explain why the materials identified so far enable phase-change based devices would hence be very beneficial. This article describes materials that have been successfully employed and dicusses common features regarding both typical structures and bonding mechanisms. It is shown that typical structural motifs and electronic properties can be found in the crystalline state that are indicative for resonant bonding, from which the employed contrast originates. The occurence of resonance is linked to the composition, thus providing a design rule for phase-change materials. This understanding helps to unravel characteristic properties such as electrical and thermal conductivity which are discussed in the subsequent section. Then, turning to the transition kinetics between the phases, the current understanding and modeling of the processes of amorphization and crystallization are discussed. Finally, present approaches for improved high-capacity optical discs and fast non-volatile electrical memories, that hold the potential to succeed present-day's Flash memory, are presented.     

Disorder-induced localization in crystalline phase-change materials

Localization of charge carriers in crystalline solids has been the subject of numerous investigations over more than half a century. Materials that show a metal-insulator transition without a structural change are therefore of interest. Mechanisms leading to metal-insulator transition include electron correlation (Mott transition) or disorder (Anderson localization), but a clear distinction is difficult. Here we report on a metal-insulator transition on increasing annealing temperature for a group of crystalline phase-change materials, where the metal-insulator transition is due to strong disorder usually associated only with amorphous solids. With pronounced disorder but weak electron correlation, these phase-change materials form an unparalleled quantum state of matter. Their universal electronic behaviour seems to be at the origin of the remarkable reproducibility of the resistance switching that is crucial to their applications in non-volatile-memory devices. Controlling the degree of disorder in crystalline phase-change materials might enable multilevel resistance states in upcoming storage devices.     

Synthesis and characterization of phase-change nanowires

Phase-change memory materials have stimulated a great deal of interest although the size-dependent behaviors have not been well studied due to the lack of method for producing their nanoscale structures. We report the synthesis and characterization of GeTe and Sb(2)Te(3) phase-change nanowires via a vapor-liquid-solid growth mechanism. The as-grown GeTe nanowires have three different types of morphologies: single-crystalline straight and helical rhombohedral GeTe nanowires and amorphous curly GeO(2) nanowires. All the Sb(2)Te(3) nanowires are single-crystalline.     

Size-dependent surface-induced heterogeneous nucleation driven phase-change in Ge2Sb2Te5 nanowires

By combining electron microscopy and size-dependent electrical measurements, we demonstrate surface-induced heterogeneous nucleation-dominant mechanism for recrystallization of amorphous phase-change Ge2Sb2Te5 nanowires. Heterogeneous nucleation theory quantitatively predicts the nucleation rates that vary by 5 orders of magnitude from 190 to 20 nm lengthscales. Our work demonstrates that increasing the surface-to-volume ratio of nanowires has two effects: lowering of the activation energy barrier due to phonon instability and providing nucleation sites for recrystallization. The systematic study of the effect of surface in phase-change behavior is critical for understanding nanoscale phase-transitions and design of nonvolatile memory devices.     

复合相变蓄热材料研究进展

相变材料是目前热门的功能材料,在储存和释放能量的过程中,温度保持不变或稳定在一定的温度区间内,使得相变材料不仅能实现热量储存且具有温度调控功能。复合相变材料由于具有多种单一材料的性质而成为研究热点,并广泛应用在建筑节能、电子器件热管理等方面。本文分类归纳了相变材料的特征,并根据化学成分不同将复合相变蓄热材料分为有机-有机、无机-无机和有机-无机三大类,结合研究现状分类梳理了不同类型复合相变蓄热材料的优缺点,并对其蓄热特性进行归纳对比。总结了复合相变蓄热材料的应用现状,结合能源应用现状和环境情况进一步分析了今后的研究和发展方向,认为未来的复合相变材料应该是高效蓄热、灵敏准确、价格低廉、环保可降解的新型复合相变材料。     

Minimum voltage for threshold switching in nanoscale phase-change memory

The size scaling of the threshold voltage required for the amorphous-to-crystalline transition in phase-change memory (PCM) is investigated using planar devices incorporating individual GeTe and Sb2Te3 nanowires. We show that the scaling law governing threshold switching changes from constant field to constant voltage scaling as the amorphous domain length falls below 10 nm. This crossover is a consequence of the energetic requirement for carrier multiplication through inelastic scattering processes and indicates that the size of PCM bits can be miniaturized to the true nanometer scale.     

Molecular memory based on nanowire-molecular wire heterostructures

This article reviews the recent research of molecular memory based on self-assembled nanowire-molecular wire heterostructures. These devices exploit a novel concept of using redox-active molecules as charge storage flash nodes for nanowire transistors, and thus boast many advantages such as room-temperature processing and nanoscale device area. Various key elements of this technology will be reviewed, including the synthesis of the nanowires and molecular wires, and fabrication and characterization of the molecular memory devices. In particular, multilevel memory has been demonstrated using In2O3 nanowires with self-assembled Fe-bis(terpyridine) molecules, which serve to multiple the charge storage density without increasing the device size. Furthermore, in-depth studies on memory devices made with different molecules or with different functionalization techniques will be reviewed and analyzed. These devices represent a conceptual breakthrough in molecular memory and may work as building blocks for future beyond-CMOS nanoelectronic circuits.     

On the p-type character of Cd-and Zn-doped InAs nanowires

InAs nanowires are potential materials for high speed nanoelectronic devices due to their high electron mobility among the semiconductor nanostructures. One of the main challenges, however, is to obtain a p-type InAs material, since the Fermi level is usually pinned at the conduction band, leading to an intrinsic n-type behaviour. Here we show through first principles calculations that InAs nanowires, doped with Cd or Zn substitutional impurities, can behave as p-type materials. Differently from other III-V nanowires, these impurities introduce shallow acceptor levels. We show that the Zn impurity can be equally distributed along the nanowire radius, naturally compensating the surface levels. On the other hand, the Cd impurity is preferentially found in the core region, requiring a surface treatment to eliminate the surface pinning levels. These results explain the available experiments and show how and why p-type InAs nanowires can be obtained.     

Microscopic origin of the fast crystallization ability of Ge-Sb-Te phase-change memory materials

Ge-Sb-Te materials are used in optical DVDs and non-volatile electronic memories (phase-change random-access memory). In both, data storage is effected by fast, reversible phase changes between crystalline and amorphous states. Despite much experimental and theoretical effort to understand the phase-change mechanism, the detailed atomistic changes involved are still unknown. Here, we describe for the first time how the entire write/erase cycle for the Ge(2)Sb(2)Te(5) composition can be reproduced using ab initio molecular-dynamics simulations. Deep insight is gained into the phase-change process; very high densities of connected square rings, characteristic of the metastable rocksalt structure, form during melt cooling and are also quenched into the amorphous phase. Their presence strongly facilitates the homogeneous crystal nucleation of Ge(2)Sb(2)Te(5). As this simulation procedure is general, the microscopic insight provided on crystal nucleation should open up new ways to develop superior phase-change memory materials, for example, faster nucleation, different compositions, doping levels and so on.     

Preparation and heat storage/release behavior of latent heat storage gypsum-based building materials

A new method to manufacture gypsum-based building materials with high latent heat storage capability is described. When expanded graphite is used as the adsorption medium for butyl stearate, an organic/inorganic phase-change composite is formed. This composite can be mixed with gypsum to manufacture a latent heat storage gypsum-based building material. Differential scanning calorimetry (DSC) test results indicate that the phase-change enthalpy value of this composite is similar to that of pure butyl stearate and that it therefore displays good thermophysical properties. We found that a mixture of gypsum with this composite should contain no more than 5 % of the latter to maintain the workability of the paste. The hardened gypsum–composite material exhibits some defects in the interface between the phase-change composite and the gypsum, but these do not seriously affect the strength of the gypsum product. The results of a temperature cycle test illustrate that gypsum containing 5 % phase-change composite can deliver high-performance heat storage/release. This characteristic of the composite will improve the inertia of ambient temperature fluctuations, making it applicable as a new building product that will conserve energy.     

Low-cost and nanoscale non-volatile memory concept for future silicon chips

Non-volatile 'flash' memories are key components of integrated circuits because they retain their data when power is interrupted. Despite their great commercial success, the semiconductor industry is searching for alternative non-volatile memories with improved performance and better opportunities for scaling down the size of memory cells. Here we demonstrate the feasibility of a new semiconductor memory concept. The individual memory cell is based on a narrow line of phase-change material. By sending low-power current pulses through the line, the phase-change material can be programmed reversibly between two distinguishable resistive states on a timescale of nanoseconds. Reducing the dimensions of the phase-change line to the nanometre scale improves the performance in terms of speed and power consumption. These advantages are achieved by the use of a doped-SbTe phase-change material. The simplicity of the concept promises that integration into a logic complementary metal oxide semiconductor (CMOS) process flow might be possible with only a few additional lithographic steps.     

Robust Room-Temperature Ferromagnetism with Giant Anisotropy in Nd-Doped ZnO Nanowire Arrays

As an important class of spintronic material, ferromagnetic oxide semiconductors are characterized with both charge and spin degrees of freedom, but they often show weak magnetism and small coercivity, which limit their applications. In this work, we synthesized Nd-doped ZnO nanowire arrays which exhibit stable room temperature ferromagnetism with a large saturation magnetic moment of 4.1 μ(B)/Nd as well as a high coercivity of 780 Oe, indicating giant magnetic anisotropy. First-principles calculations reveal that the remarkable magnetic properties in Nd-doped ZnO nanowires can be ascribed to the intricate interplay between the spin moments and the Nd-derived orbital moments. Our complementary experimental and theoretical results suggest that these magnetic oxide nanowires obtained by the bottom-up synthesis are promising as nanoscale building blocks in spintronic devices.