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Phase change in GeTe/Sb2Te3 superlattices: Formation of the vacancy-ordered metastable cubic structure via Ge migration
Abstract
Interfacial phase-change memory (iPCM), comprising alternating layers of two chalcogenide-based phase-change materials—Sb2Te3 (ST) and GeTe (GT)—has demonstrated outstanding performance in resistive memories. However, its comprehensive understanding is controversial. Herein, the phase-change characteristic of iPCM is identified using atomic scale imaging, X-ray diffraction, and chemical analysis with first-principles density functional theory (DFT) calculations. By inducing laser pulsing, the ST/GT superlattice structure in the low-resistance state tends to reversibly convert into the modified metastable face-centered cubic (fcc) GeSbTe structure in the high-resistance state. This transition is driven by Ge atom rearrangement to pre-existing vacancy layers and ordered vacancy-layer formation. DFT atomistic modeling shows that the resistance difference of 10² orders between low- and high-resistance states is a direct consequence of the intercalation of Ge atoms into the vacancy layer. These results provide insights into iPCM phase-change mechanisms and phase-change random access memory design with low energy and high speed.
... In GST alloy, phase change occurs with reversible switching between octahedral and tetrahedral motifs of Ge atom. Similar phase change process with Ge atoms have been reported for GT/ST SL. 28 The difference is that the phase change process in the superlattice structure is limited to the area near interface (vdW gap), hence reducing entropic loss compared to GST alloy. 7 To investigate the change in the local structure of Ge atoms at the vdW interface using DFT calculations, unit cells of GT/(Ti)-ST SL were constructed using Ferro structure taking Ge/Sb intermixing 17 into account to reflect the experimental environment. ...
Interfacial Phase Change Memory (iPCM) retrench unnecessary power consumption due to wasted heat generated during phase change by reducing unnecessary entropic loss. In this study, an advanced iPCM (GeTe/Ti-Sb2Te3 Superlattice) is synthesized by doping Ti into Sb2Te3. Structural analysis and density functional theory (DFT) calculations confirm that bonding distortion and structurally well-confined layers contribute to improve phase change properties in iPCM. Ti-Sb2Te3 acts as an effective thermal barrier to localize the generated heat inside active region, which leads to reduction of switching energy. Since Ge-Te bonds adjacent to short and strong Ti-Te bonds are more elongated than the bonds near Sb-Te, it is easier for Ge atoms to break the bond with Te due to strengthened Peierls distortions (Rlong/Rshort) during phase change process. Properties of advanced iPCM (cycling endurance, write speed/energy) exceed previous records. Moreover, well-confined multi-level states are obtained with advanced iPCM, showing potential as a neuromorphic memory. Our work paves the way for designing superlattice based PCM by controlling confinement layers.
... 30 SET and RESET phases of the superlattices. 33 It is a notable result that spontaneous transition from octahedron to tetrahedron has been achieved during the structural relaxation of the superlattices. These results directly suggest that about 30% of the content of Ge in tetrahedron drastically changes the type of the bond which is consistent with the experimentally estimated value of the contents (30%) in the alloys via structural analysis. ...
Reversible conversion over multi-million-times in bond types between metavalent and covalent bonds becomes one of the most promising bases for universal memory. As the conversions have been found in metastable states, extended category of crystal structures from stable states via redistribution of vacancies, researches on kinetic behavior of the vacancies are highly on demand. However, they remain lacking due to difficulties with experimental analysis. Herein, the direct observation of the evolution of chemical states of vacancies clarifies the behavior by combining analysis on charge density distribution, electrical conductivity, and crystal structures. Site-switching of vacancies gradually occurs with diverged energy barriers owing to a unique activation code-the accumulation of vacancies triggers spontaneous gliding along atomic planes to relieve electrostatic repulsion. Study on the behavior can be further applied to multi-phase superlattices composed of Sb2Te3 (2D) and GeTe (3D) sublayers, which represent the superior memory performances but their operating mechanisms were still under debates due to their complexity. The site-switching is favorable (suppressed) when Te-Te bonds are formed as physisorption (chemisorption) over the interface between Sb2Te3 (2D) and GeTe (3D) sublayers driven by configurational entropic gain (electrostatic enthalpic loss). Depending on the type of interfaces between sublayers, phases of the superlattices are classified into metastable and stable states, where the conversion could be only achieved in the metastable state. From this comprehensive understanding on the operating mechanism via kinetic behaviors of vacancies and the metastability, further studies towards vacancy engineering are expected in versatile materials.
Reversible conversion over multimillion times in bond types between metavalent and covalent bonds becomes one of the most promising bases for universal memory. As the conversions have been found in metastable states, an extended category of crystal structures from stable states via redistribution of vacancies, research on kinetic behavior of the vacancies is highly in demand. However, it remains lacking due to difficulties with experimental analysis. Herein, the direct observation of the evolution of chemical states of vacancies clarifies the behavior by combining analysis on charge density distribution, electrical conductivity, and crystal structures. Site-switching of vacancies of Sb2Te3 gradually occurs with diverged energy barriers owing to their own activation code: the accumulation of vacancies triggers spontaneous gliding along atomic planes to relieve electrostatic repulsion. Studies on the behavior can be further applied to multiphase superlattices composed of Sb2Te3 (2D) and GeTe (3D) sublayers, which represent superior memory performances, but their operating mechanisms were still under debate due to their complexity. The site-switching is favorable (suppressed) when Te-Te bonds are formed as physisorption (chemisorption) over the interface between Sb2Te3 (2D) and GeTe (3D) sublayers driven by configurational entropic gain (electrostatic enthalpic loss). Depending on the type of interfaces between sublayers, phases of the superlattices are classified into metastable and stable states, where the conversion could only be achieved in the metastable state. From this comprehensive understanding on the operating mechanism via kinetic behaviors of vacancies and the metastability, further studies toward vacancy engineering are expected in versatile materials.
Single element switch
Phase-change materials are attractive for computer memory and switching, in part due to their small size and fast switching speeds. However, competitive materials frequently have many elements, which decreases the switching reliability. Shen et al . built a pure tellurium device that is capable of fast switching through a phase transformation (see the Perspective by Calarco and Arciprete). Unlike many other phase-change materials, the change in resistance happens because the tellurium melts during the switching process. The resulting device can be switched 100 million times before failure and is an appealing route for avoiding the issues from multi-element phase-change materials. —BG
By controlling the amorphous-to-crystalline relative volume, chalcogenide phase-change memory materials can provide multi-level data storage (MLS), which offers great potential for high-density storage-class memory and neuro-inspired computing. However, this type of MLS system suffers from high power consumption and a severe time-dependent resistance increase (“drift”) in the amorphous phase, which limits the number of attainable storage levels. Here, we report a new type of MLS system in yttrium-doped antimony telluride, utilizing reversible multi-level phase transitions between three states, i.e., amorphous, metastable cubic and stable hexagonal crystalline phases, with ultralow power consumption (0.6 – 4.3 pJ) and ultralow resistance drift for the lower two states (power-law exponent < 0.007). The metastable cubic phase is stabilized by yttrium, while the evident reversible cubic-to-hexagonal transition is attributed to the sequential and directional migration of Sb atoms. Finally, the decreased heat dissipation of the material and the increase in crystallinity contribute to the overall high performance. This study opens a new way to achieve advanced multi-level phase-change memory without the need for complicated manufacturing procedures or iterative programming operations.
Tailoring the degree of disorder in chalcogenide phase‐change materials (PCMs) plays an essential role in nonvolatile memory devices and neuro‐inspired computing. Upon rapid crystallization from the amorphous phase, the flagship Ge–Sb–Te PCMs form metastable rocksalt‐like structures with an unconventionally high concentration of vacancies, which results in disordered crystals exhibiting Anderson‐insulating transport behavior. Here, ab initio simulations and transport experiments are combined to extend these concepts to the parent compound of Ge–Sb–Te alloys, viz., binary Sb2Te3, in the metastable rocksalt‐type modification. Then a systematic computational screening over a wide range of homologous, binary and ternary chalcogenides, elucidating the critical factors that affect the stability of the rocksalt structure is carried out. The findings vastly expand the family of disorder‐controlled main‐group chalcogenides toward many more compositions with a tunable bandgap size for demanding phase‐change applications, as well as a varying strength of spin–orbit interaction for the exploration of potential topological Anderson insulators.
Traditional von Neumann computing architecture with separated computation and storage units has already impeded the data processing performance and energy efficiency, calling for emerging neuromorphic electronic and optical devices and systems which can mimic the human brain to shift this paradigm. Material-level innovation has become the key component to this revolution of information technology. Chalcogenide phase-change material (PCM) as a well-acknowledged data-storage medium is a promising candidate to tackle this challenge. In this review, the use of PCMs to implement artificial neurons and synapses from both the electronic and optical respects is discussed, and in particular, the structure-property physics and transition dynamics that enable such brain-inspired and in-memory computing applications are emphasized. Recent advances on the atomic-level amorphous and crystalline structures, transition mechanisms, materials optimization and design, neural and synaptic devices, brain-inspired chips, and computing systems, as well as the future opportunities of PCMs, are summarized and discussed.
The global demand for data storage and processing is increasing exponentially. To deal with this challenge, massive efforts have been devoted to the development of advanced memory and computing technologies. Chalcogenide phase-change materials (PCMs) are currently at the forefront of this endeavor. In this Review, we focus on the mechanisms of the spontaneous structural relaxation – aging – of amorphous PCMs, which causes the well-known resistance drift issue that significantly reduces the device accuracy needed for phase-change memory and computing applications. We review the recent breakthroughs in uncovering the structural origin, achieved through state-of-the-art experiments and ab initio atomistic simulations. Emphasis will be placed on the evolving atomic-level details during the relaxation of the complex amorphous structure. We also highlight emerging strategies to control aging, inspired by the in-depth structural understanding, from both materials science and device engineering standpoints, that offer effective solutions to reduce the resistance drift. In addition, we discuss an important new paradigm – machine learning – and the potential power it brings in interrogating amorphous PCMs as well as other disordered alloy systems. Finally, we present an outlook to comment on future research opportunities in amorphous PCMs, as well as on their reduced aging tendency in other advanced applications such as non-volatile photonics.
GeTe is a potential thermoelectric material for mid-temperature range applications. Here, we report on GeTe and Ge0.9Sn0.1Te prepared using a fast and simple arc-melting method. Their crystal structures have been analyzed by synchrotron X-ray diffraction. Calorimetry identified a shift in the rhombohedral to cubic structural transition temperature from 700 K to 557 K due to Sn alloying. Nevertheless, the temperature of the maximum Seebeck-coefficient is preserved, at 770 K. The thermoelectric properties are also reported, with a strong decrease of electric and thermal conductivities of the Sn-doped compound, as compared to the undoped one. The Hall-mobility also decreases strongly upon doping.
Unconventionally high amount of atomic vacancies up to more than 10% are known to form in Ge-Sb-Te crystals upon rapid crystallization from the amorphous phase. Upon thermal annealing, an ordering process of these atomic vacancies is observed, triggering a structural transition from the recrystallized rocksalt structure to a stable layered trigonal structure and a transition from insulator to metal. In this work, we demonstrate an opposite vacancy disordering process upon extensive electron beam irradiation, which is accompanied by the reverse transition from the stable trigonal phase to the metastable cubic phase. The combined in situ transmission electron microscopy experiments and density functional theory nudged elastic band calculations reveal three transition stages, including (I) the vacancy diffusion in the trigonal phase, (II) the change in atomic stacking, and (III) the disappearance of vacancy-rich planes. The mechanism of vacancy disordering is attributed to kinetic knock-on collision effects of the high-energy electron beam, which prevail over the heating effects.
Phase-change memories based on reversible amorphous-crystal transformations in pseudobinary GeTe-Sb2Te3 alloys are one of the most promising nonvolatile memory technologies. The recently proposed superlattice-based memory, or interfacial phase-change memory (iPCM), is characterized by significantly faster switching, lower energy consumption, and better endurance. The switching mechanism in iPCM, where both the SET and RESET states are crystalline, is still contentious. Here, using the ab initio density functional theory simulations, a conceptually new switching mechanism for iPCM is derived, which is based on the change in the potential landscape of the bandgap, associated with local deviations from the pseudobinary stoichiometry across the van der Waals gaps and the associated shift of the Fermi level. The crucial role in this process belongs to Ge/Sb intermixing on the cation planes of iPCM. These findings offer a comprehensive understanding of the switching mechanisms in iPCM and are an essential step forward to the insightful development of phase-change memory technology.
GeTe-Sb2Te3 pseudobinary system, especially Ge2Sb2Te5 alloy, is the most desirable material to be commercialized in phase change random access memory. Directly resolving the local atomic arrangement of Ge2Sb2Te5 during intermediate steps is an effective method to understand its transition mechanism from face-centered-cubic to hexagonal phases. In this study, we provide insights into the atomic arrangement variation during face-centered-cubic to hexagonal transition process in Ge2Sb2Te5 alloy by using advanced atomic resolution energy dispersive X-ray spectroscopy. Induced by thermal annealing, randomly distributed germanium and antimony atoms would migrate to the specific (111) layer in different behaviors, and antimony atoms migrate earlier than germanium atoms during the phase transition process, gradually forming intermediate structures similar to hexagonal lattice. With the migration completed, the obtained stable hexagonal structure has a partially ordered stacking sequence described as below: -Te-Sbx/Gey-Te-Gex/Sby-Te-Gex/Sby-Te-Sbx/Gey-Te- (x > y), which is directly related to the migration process. The current visual fragments suggest a gradual transition mechanism, and guide the performance optimization of Ge2Sb2Te5 alloy.
Nonvolatile memory, of which phase-change memory (PCM) is a leading technology, is currently a key element of various electronics and portable systems. An important step in the development of conceptually new devices is the class of van der Waals (vdW)-bonded GeTe/Sb2Te3 superlattices (SLs). With their order of magnitude faster switching rates and lower energy consumption compared to those of alloy-based devices, they are widely regarded as the next step in the implementation of PCM. In contrast to conventional PCM, where the SET and RESET states arise from the crystalline and amorphous phases, in SLs, both the SET and RESET states remain crystalline. In an earlier work, the superior performance of SLs was attributed to the reduction of entropic losses associated with the one-dimensional motion of interfacial Ge atoms located in the vicinity of Sb2Te3 quintuple layers. Subsequent experimental studies using transmission electron microscopy revealed that GeTe and Sb2Te3 blocks strongly intermix during the growth of the GeTe phase, challenging the original proposal but at the same time raising new fundamental issues. In this work, we propose a new approach to switching in SLs associated with the reconfiguration of vdW gaps accompanied by local deviation of stoichiometry from the GeTe/Sb2Te3 quasibinary alloys. The model resolves in a natural way the existing controversies, explains the large conductivity contrast between the SET and RESET crystalline states, is not compromised by Ge/Sb intermixing, and provides a new perspective for the industrial development of memory devices based on such SLs. The proposed concept of vdW gap reconfiguration may also be applicable to designing a broad variety of engineered two-dimensional vdW solids.
GeSbTe-based chalcogenide superlattice (CSLs) phase-change memories consist of GeSbTe layer blocks separated by van der Waals bonding gaps. Recent high resolution electron microscopy found two types of disorder in CSLs, a chemical disorder within individual layers, and SbTe bilayer stacking faults connecting one block to an adjacent block which allows individual block heights to vary. The disorder requires a generalization of the previous switching models developed for CSL systems. Density functional calculations are used to describe the stability of various types of intra-layer disorder, how the block heights can vary by means of SbTe-based stacking faults and using a vacancy-mediated kink motion, and also to understand the nature of the switching process in more chemically disordered CSLs.
Strain engineering is an emerging route for tuning the bandgap, carrier mobility, chemical reactivity and diffusivity of materials. Here we show how strain can be used to control atomic diffusion in van der Waals heterostructures of two-dimensional (2D) crystals. We use strain to increase the diffusivity of Ge and Te atoms that are confined to 5 Å thick 2D planes within an Sb2 Te3-GeTe van der Waals superlattice. The number of quintuple Sb2 Te3 2D crystal layers dictates the strain in the GeTe layers and consequently its diffusive atomic disordering. By identifying four critical rules for the superlattice configuration we lay the foundation for a generalizable approach to the design of switchable van der Waals heterostructures. As Sb2 Te3-GeTe is a topological insulator, we envision these rules enabling methods to control spin and topological properties of materials in reversible and energy efficient ways.
A two-step growth method is proposed for the fabrication of highly-oriented Sb2Te3 and related superlattice films using sputtering. We report that the quality and grain size of Sb2Te3 as well as GeTe/Sb2Te3superlattice films strongly depend on the thickness of the room-temperature deposited and subsequently by annealing at 523 K Sb2Te3 seed layer. This result may open up new possibilities for the fabrication of two-dimensional electronic devices using layered chalcogenides.
Phase Change Materials (PCMs) are unique compounds employed in non-volatile random access memory thanks to the rapid and reversible transformation between the amorphous and crystalline state that display large differences in electrical and optical properties. In addition to the amorphous-to-crystalline transition, experimental results on polycrystalline GeSbTe alloys (GST) films evidenced a Metal-Insulator Transition (MIT) attributed to disorder in the crystalline phase. Here we report on a fundamental advance in the fabrication of GST with out-of-plane stacking of ordered vacancy layers by means of three distinct methods: Molecular Beam Epitaxy, thermal annealing and application of femtosecond laser pulses. We assess the degree of vacancy ordering and explicitly correlate it with the MIT. We further tune the ordering in a controlled fashion attaining a large range of resistivity. Employing ordered GST might allow the realization of cells with larger programming windows.
The technological success of phase-change materials in the field of data storage and functional systems stems from their distinctive electronic and structural peculiarities on the nanoscale. Recently, superlattice structures have been demonstrated to dramatically improve the optical and electrical performances of these chalcogenide based phase-change materials. In this perspective, unravelling the atomistic structure that originates the improvements in switching time and switching energy is paramount in order to design nanoscale structures with even enhanced functional properties. This study reveals a high- resolution atomistic insight of the [GeTe/Sb2Te3] interfacial structure by means of Extended X-Ray Absorption Fine Structure spectroscopy and Transmission Electron Microscopy. Based on our results we propose a consistent novel structure for this kind of chalcogenide superlattices.
Van der Waals heterostructure superlattices of Sb2 Te1 and GeTe are strain engineered to promote switchable atomic disordering, which is confined to the GeTe layer. Careful control of the strain in the structures presents a new degree of freedom to design the properties of functional superlattice structures for data storage and photonics applications.
GeTe-Sb2Te3 superlattices are nanostructured phase-change materials which are under intense investigation for non-volatile memory applications. They show superior properties compared to their bulk counterparts and significant efforts exist to explain the atomistic nature of their functionality. The present work sheds new light on the interface formation between GeTe and Sb2Te3, contradicting previously proposed models in the literature. For this purpose [GeTe(1 nm)-Sb2Te3(3 nm)]15 superlattices were grown on passivated Si(111) at 230 °C using molecular beam epitaxy and they have been characterized particularly with cross-sectional HAADF scanning transmission electron microscopy. Contrary to the previously proposed models, it is found that the ground state of the film actually consists of van der Waals bonded layers (i.e. a van der Waals heterostructure) of Sb2Te3 and rhombohedral GeSbTe. Moreover, it is shown by annealing the film at 400 °C, which reconfigures the superlattice into bulk rhombohedral GeSbTe, that this van der Waals layer is thermodynamically favored. These results are explained in terms of the bonding dimensionality of GeTe and Sb2Te3 and the strong tendency of these materials to intermix. The findings debate the previously proposed switching mechanisms of superlattice phase-change materials and give new insights in their possible memory application.
We study the switching process in chalcogenide superlattice (CSL) phase-change memory materials by describing the motion of an atomic layer between the low and high resistance states. Two models have been proposed by different groups based on high-resolution electron microscope images. Model 1 proposes a transition from Ferro to Inverted Petrov state. Model 2 proposes a switch between Petrov and Inverted Petrov states. For each case, we note that the main transition is actually a vertical displacement of a Ge layer through a Te layer, followed by a lateral motion of GeTe sublayer to the final, low energy structure. Through calculating energy barriers, the rate-determining step is the displacive transition.
A superlattice made of a topological insulator (Sb2Te3) and a normal insulator (ferroelectric GeTe), also called an interfacial phase-change material, are switched between the Dirac semimetal and gapped phases by applying an external electric field, which provides a platform to study topological insulators and opens new possibilities for designing phase-change memory devices. © 2013 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Changes in the electronic structures of Ge2Sb2Te5 (GST) and N-doped Ge2Sb2Te5 film during the phase transition from an amorphous to a crystalline phase were studied using synchrotron radiation high-resolution x-ray photoemission spectroscopy. The changes in tetrahedral and octahedral coordinated Ge 3d peaks are closely related to the changes in the chemical bonding state of GST films. The metallic Sb peak in the Sb 4d spectra of annealed GST films demonstrates that the metallic Sb atoms become segregated during thermal treatment resulting in phase separation. The incorporation of nitrogen into the GST film affects its structure and chemical bonding state, resulting in the suppression of crystallization. The incorporation of nitrogen also increases the optical band gap of the film due to the formation of a nitride.
The study of metal-insulator transitions (MITs) in crystalline solids is a subject of paramount importance, both from the fundamental point of view and for its relevance to the transport properties of materials. Recently, a MIT governed by disorder was observed in crystalline phase-change materials. Here we report on calculations employing density functional theory, which identify the microscopic mechanism that localizes the wavefunctions and is driving this transition. We show that, in the insulating phase, the electronic states responsible for charge transport are localized inside regions having large vacancy concentrations. The transition to the metallic state is driven by the dissolution of these vacancy clusters and the formation of ordered vacancy layers. These results provide important insights on controlling the wavefunction localization, which should help to develop conceptually new devices based on multiple resistance states.
We present an efficient scheme for calculating the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrices will be discussed. Our approach is stable, reliable, and minimizes the number of order N-atoms(3) operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special ''metric'' and a special ''preconditioning'' optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent calculations. It will be shown that the number of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order N-atoms(2) scaling is found for systems up to 100 electrons. If we take into account that the number of k points can be implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large number of different systems (liquid and amorphous semiconductors, liquid simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable.
The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Blöchl's projector augmented wave (PAW) method is derived. It is shown that the total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addition, critical tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed core all electron methods. These tests include small molecules (H2, H2O, Li2, N2, F2, BF3, SiF4) and several bulk systems (diamond, Si, V, Li, Ca, CaF2, Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
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.
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.
Present-day multimedia strongly rely on rewritable phase-change optical memories. We demonstrate that, different from the current consensus, Ge(2)Sb(2)Te(5), the material of choice in DVD-RAM, does not possess the rocksalt structure but more likely consists of well-defined rigid building blocks that are randomly oriented in space consistent with cubic symmetry. Laser-induced amorphization results in drastic shortening of covalent bonds and a decrease in the mean-square relative displacement, demonstrating a substantial increase in the degree of short-range ordering, in sharp contrast to the amorphization of typical covalently bonded solids. This novel order-disorder transition is due to an umbrella-flip of Ge atoms from an octahedral position into a tetrahedral position without rupture of strong covalent bonds. It is this unique two-state nature of the transformation that ensures fast DVD performance and repeatable switching over ten million cycles.
Chalcogenide superlattice (CSL) is one of the emerging material technologies for ultralow-power phase change memories. However, the resistance switching mechanism of the CSL-based device is still hotly debated. Early electrical measurements and recent materials characterizations have suggested that the Kooi-phase CSL is very likely to be the as-fabricated low-resistance state. Due to the difficulty in in situ characterization at atomic resolution, the structure of the electrically switched CSL in its high-resistance state is still unknown and mainly investigated by theoretical modelings. So far, there has been no simple model that can unify experimental results obtained from device-level electrical measurements and atomic-level materials characterizations. In this work, we carry out atomistic transport modelings of the CSL-based device and propose a simple mechanism accounting for its high resistance. The modeled high-resistance state is based on the interfacial SbTe bilayer flipped CSL that has previously been mistaken for the low-resistance state. This work advances the understanding of CSL for emerging memory applications.
Sb2Te3 is a very promising phase-change material due to its fast reversible phase transition between the amorphous and crystal phases. Crystalline Sb2Te3 can adopt the cubic (rock-salt) or rhombohedral structure, and for the cubic Sb2Te3 which is metastable, 33.3% vacancies exist in the Sb sublattice. The intrinsic vacancies which normally have significant effects on the fundamental property of the phase-change material need to be thoroughly studied for the practical application of Sb2Te3. In this work, by using ab initio calculations, various configurations of the vacancies with different randomness as well as their effects on the electronic property and phase transition of cubic Sb2Te3 are investigated. We found that the vacancy configurations that have rather small energy difference can exhibit contrast electronic property and different localized states near Fermi level. Furthermore, the migration of Sb atom and the lattice transformation accounting for the phase transition between cubic and rhombohedral Sb2Te3 have smaller energy barrier than those in Ge-Sb-Te compound, which should be responsible for the metastability of cubic Sb2Te3 and its rapid transition to the rhombohedral phase. Our results provide a comprehensive understanding of cubic Sb2Te3 and may offer new insight into the development of phase-change memory based on Sb2Te3.
The nanosize confined effect is believed to contribute to improving the resistance drift in nanophase change devices. However, the smaller dimension of device designs is limited by plane lithography techniques. Phase change memory with a confined thickness of ultrathin GeTe layers is fabricated to overcome the limit of current plane lithography. Those memory cells composed of two-dimensional materials present a suppressed resistance drift in their amorphous phase. The drift exponent ν is reduced to 0.05 for 3 nm GeTe layers. Combined with Raman spectroscopy and ab initio molecular dynamics simulations, the structural relaxation process is described as the decay of tetrahedral-bonded sites. Tetrahedrons in ultrathin films are more stable than those in bulk materials. The local motifs of amorphous GeTe ultrathin films are covalently bonded and highly ordered in a short range. The majority of highly ordered tetrahedral clusters prevents spontaneous structural relaxation and leads to high stability in amorphous states, which helps to stop intrinsic fluctuations in physical properties of SET and RESET states, without an extra processing cost.
Traditional von Neumann computing systems involve separate processing and memory units. However, data movement is costly in terms of time and energy and this problem is aggravated by the recent explosive growth in highly data-centric applications related to artificial intelligence. This calls for a radical departure from the traditional systems and one such non-von Neumann computational approach is in-memory computing. Hereby certain computational tasks are performed in place in the memory itself by exploiting the physical attributes of the memory devices. Both charge-based and resistance-based memory devices are being explored for in-memory computing. In this Review, we provide a broad overview of the key computational primitives enabled by these memory devices as well as their applications spanning scientific computing, signal processing, optimization, machine learning, deep learning and stochastic computing.
Ge/Sb atomic intermixing in interfacial cationic layers is a common phenomenon for GeTe-Sb2Te3 superlattice (GST-SL) used in memory devices. In this paper, we explored the effect of Ge/Sb intermixing on the phase change behavior of GST-SL upon the heating-quenching procedure. Four interfacial intermixing models of Kooi, Ferro, Petrov and Inverted Petrov with different Ge/Sb intermixing ratios (25/75, 50/50 and 75/25) were developed based on the ab initio molecular dynamics. The structural evolution indicated that the Ge/Sb interfacial intermixing could facilitate the structure changes especially for 50/50 Ge/Sb intermixed models. When quenching from 1500 K, more 4-fold Ge-centered octahedrons were produced than tetrahedrons, and the electron localization function further proved that the distorted of Ge(Sb)-centered 6-fold octahedrons were caused by the asymmetrical interactions of Ge-Ge/Sb and Ge-Te. A relatively large Te p orbital contribution in coexisted Ge/Te layer led to a narrower bandgap. In addition, different Ge/Sb atom intermixed ratio which affected the electronic local structure, led to the discrepancy in the initial atom movement of Sb or Ge movement near the gap. The present studies enrich the understanding of Ge/Sb interfacial atomic intermixing effects in GST-SL structural changes.
Van der Waals (vdW) layered GeTe-Sb2Te3 superlattices (GST-SL) have attracted enormous attentions due to the ultralow power consumption for nonvolatile phase change memory. In this paper, effects of biaxial strain on interfacial intermixing and local structures in strain engineered GST-SL were studied. Highly (0 0 l) textured GST-SL with thickness-varied Sb2Te3 sublayers were fabricated by magnetron sputtering and investigated with multiple analyses on surfaces and interfaces. The appearance of Ge-Sb-Te alloys indicated the interfacial Ge/Sb intermixing in strain engineered GST-SL, which actually were composed of Sb2Te3 quintuple layers, Ge-Sb-Te vdW layers and isolated GeTe bilayers. Grazing incidence x-ray diffraction (GID) and x-ray photoelectron spectroscopy (XPS) results revealed that biaxial strain not only facilitated the interfacial intermixing, but also caused the reconfiguration of Ge-Sb-Te vdW layers. Raman spectra indicated that vertical and in-plane vibrations of GeTe layers were not affected by the interfacial intermixing and the newly-formed Ge-Sb-Te layers had similar vibration characteristics as that of GeTe layers. A modified switching mechanism of GST-SL, relating to both the amorphous-crystalline phase transition of GeTe and Ge-Sb-Te layers incorporated into the Sb2Te3 matrix, was then presented. The present studies shed new light on strain engineering for GST-SL and indicate their potential optoelectronic applications.
Phase change superlattice is one of the emerging material technologies for ultra-low power phase change memories. However, the resistance switching mechanisms of phase change superlattice are still hotly debated. Besides interfacial crystalline phase change and bulk crystalline-to-amorphous phase change, the possibility of filamentary switching cannot be ruled out. Here, we study the atomic and electronic structures of Te and Sb native filaments embedded in the host Ge2Sb2Te5 superlattices. Te and Sb have compatible structures to Ge2Sb2Te5 superlattice with lower band gap values. In addition, the filament-to-dielectric interfaces can inherently be carrier excessive. These indicate that Te or Sb filament is likely to form and leads to considerable decrease of the resistance locally.
Phase Change Memory (PCM) is a leading candidate for next generation data storage, but it typically suffers from high switching (RESET) current density (20–30 MA/cm²). Interfacial Phase Change Memory (IPCM) is a type of PCM using multilayers of Sb2Te3/GeTe, with up to 100× lower reported RESET current compared to the standard Ge2Sb2Te5-based PCM. Several hypotheses involving fundamentally new switching mechanisms have been proposed to explain the low switching current densities, but consensus is lacking. Here, we investigate IPCM switching by analyzing its thermal, electrical, and fabrication dependencies. First, we measure the effective thermal conductivity (∼0.4 W m−1 K⁻¹) and thermal boundary resistance (∼3.4 m² K GW⁻¹) of Sb2Te3/GeTe multilayers. Simulations show that IPCM thermal properties account only for an ∼13% reduction of current vs standard PCM and cannot explain previously reported results. Interestingly, electrical measurements reveal that our IPCM RESET indeed occurs by a melt-quench process, similar to PCM. Finally, we find that high deposition temperature causes defects including surface roughness and voids within the multilayer films. Thus, the substantial RESET current reduction of IPCM appears to be caused by voids within the multilayers, which migrate to the bottom electrode interface by thermophoresis, reducing the effective contact area. These results shed light on the IPCM switching mechanism, suggesting that an improved control of layer deposition is necessary to obtain reliable switching.
Chalcogenide-based thin films are employed in data storage and memory technology whereas van der Waals bonded layered chalcogenide heterostructures are considered as a main contender for memory devices with low power consumption. The reduction of switching energy is due to the lowering of entropic losses governed by restricted motion of atoms in one dimension within the crystalline states. The investigations of switching mechanisms in such superlattices have recently attracted much attention and the proposed models are still under debate. This is partially due to the lack of direct observation of atomic scale processes, which might occur in these chalcogenide systems. This work reports a direct, nanoscale observations of the order-disorder processes in van der Waals bonded Ge-Sb-Te thin films and GeTe-Sb2Te3 based superlattices using in situ experiments inside an aberration-corrected transmission electron microscope. The findings reveal reversible self-assembled reconfiguration of structural order in those materials. The process is associated with ordering of randomly distributed vacancies within of the studied materials into ordered vacancy layers and with readjustment of lattice plane distances within the newly formed layered structures, showing high flexibility of the layered chalcogenide-based systems. Thus, the ordering process results in the formation of vacancy-bonded building blocks intercalated within of van der Waals bonded units. Moreover, vacancy-bonded building blocks can be reconfigured to the initial structure under influence of the electron beam, while in situ targeted electron beam exposure of the recovered layers lead to the reverse process. Overall, the outcomes provide new insights into local structure and switching mechanism in chalcogenide superlattices.
Two-dimensional van-der-Waals-bonded chalcogenide heterostructures have recently received a lot of attention due to promising applications in the fields of photonics, plasmonics and data storage. Of particular interest is the interfacial switching process inherent in these structures, which is assumed to occur locally at the van-der-Waals interfaces and thus represents an intracrystalline transition. However, detailed experimental studies on the underlying mechanism are still lacking. In this work, epitaxially grown thin films consisting of van-der-Waals-bonded Ge-Sb-Te and GeTe/Sb2Te3 based heterostructures are employed as a model system to investigate structural changes induced by a single ns-laser pulse. A combined approach using X-ray diffraction and advanced transmission electron microscopy is applied to study phase
transitions within the Ge-Sb-Te-based thin films in detail. The results reveal ultrafast transitions from 2D-bonded layered structures to 3D-bonded structures via a transient molten phase. Moreover, the interface between the 2D- and 3D-bonded structures is well defined by a single van-der-Waals gap, suggesting that the transition can be controlled very precisely in its spatial extent by an appropriate choice of the laser fluence. Overall, the results of this work offer a new perspective on the switching mechanism in Ge-Sb-Te-based materials and demonstrate the potential of van-der-Waals-bonded Ge-Sb-Te
compounds to be applied for novel phase-change memory concepts.
Van der Waals layered GeTe/Sb2Te3 superlattices (SLs) have demonstrated outstanding performances for use in resistive memories in so‐called interfacial phase‐change memory (iPCM) devices. GeTe/Sb2Te3 SLs are made by periodically stacking ultrathin GeTe and Sb2Te3 crystalline layers. The mechanism of the resistance change in iPCM devices is still highly debated. Recent experimental studies on SLs grown by molecular beam epitaxy or pulsed laser deposition indicate that the local structure does not correspond to any of the previously proposed structural models. Here, a new insight is given into the complex structure of prototypical GeTe/Sb2Te3 SLs deposited by magnetron sputtering, which is the used industrial technique for SL growth in iPCM devices. X‐ray diffraction analysis shows that the structural quality of the SL depends critically on its stoichiometry. Moreover, high‐angle annular dark‐field‐scanning transmission electron microscopy analysis of the local atomic order in a perfectly stoichiometric SL reveals the absence of GeTe layers, and that Ge atoms intermix with Sb atoms in, for instance, Ge2Sb2Te5 blocks. This result shows that an alternative structural model is required to explain the origin of the electrical contrast and the nature of the resistive switching mechanism observed in iPCM devices.
BoltzTraP2 is a software package for calculating a smoothed Fourier expression of periodic functions and the Onsager transport coefficients for extended systems using the linearized Boltzmann transport equation. It uses only the band and $k$-dependent quasi-particle energies, as well as the intra-band optical matrix elements and scattering rates, as input. The code can be used via a command-line interface and/or as a Python module. It is tested and illustrated on a simple parabolic band example as well as silicon. The positive Seebeck coefficient of lithium is reproduced in an example of going beyond the constant relaxation time approximation.
Interfacial phase change memory (iPCM) based on GeTe and Sb2Te3 superlattices (SLs) is an emerging contender for non-volatile data storage applications. A detailed knowledge of the atomic structure of these materials is crucial for further development of SLs and for a better understanding of the resistivity switching characteristics of iPCM devices. In this work, crystalline GeTe-Sb2Te3-based SLs, produced by pulsed laser deposition onto a Si(111) substrate at temperatures lower than in previous studies, are analyzed by advanced scanning transmission electron microscopy. The results reveal the formation of Ge-rich Ge(x+y)Sb(2–y)Tez building blocks with specific numbers of ordered Ge cation layers (between 1 and 5) and disordered cation layers (4) for z = 6–10, as well as intermixed cation layers for z = 5, within the SLs. The G Ge(x+y)Sb(2–y)Tez units are separated from the Sb2Te3 building blocks by van der Waals gaps. In particular, the interlayer bonding is promoted by the formation of outermost cation layers consisting of intermixed GeSb within the building blocks adjacent to the van der Waals gaps. The Ge(x+y)Sb(2–y)Tez units with z > 5 retain metastable crystal structures with two-dimensional bonding within the SLs. The present study shed new light on the possible configurations of the building units that can be formed during the synthesis of GeTe-Sb2Te3-based iPCM materials. In addition, a possible switching mechanism active in iPCM materials is discussed.
Phase-change materials based on GeSbTe show unique switchable optoelectronic properties and are an important contender for next-generation non-volatile memories. Moreover, they recently received considerable scientific interest, because it is found that a vacancy ordering process is responsible for both an electronic metal-insulator transition and a structural cubic-to-trigonal transition. GeTe-Sb2Te3 based superlattices, or specifically their interfaces, provide an interesting platform for the study of GeSbTe alloys. In this work such superlattices have been grown with molecular beam epitaxy and they have been characterized extensively with transmission electron microscopy and x-ray diffraction. It is shown that the van der Waals gaps in these superlattices, which result from vacancy ordering, are mobile and reconfigure through the film using bi-layer defects and Ge diffusion upon annealing. Moreover, it is shown that for an average composition that is close to GeSb2Te4 a large portion of 9-layered van der Waals systems is formed, suggesting that still a substantial amount of random vacancies must be present within the trigonal GeSbTe layers. Overall these results illuminate the structural organization of van der Waals gaps commonly encountered in GeSbTe alloys, which are intimately related to their electronic properties and the metal-insulator transition.
GeTe–Sb2Te3 superlattices have attracted major interest in the field of phase-change memories due to their improved properties compared with their mixed counterparts. However, their crystal structure and resistance-switching mechanism are currently not clearly understood. In this work epitaxial GeTe–Sb2Te3 superlattices have been grown with different techniques and were thoroughly investigated to unravel the structure of their crystalline state with particular focus on atomic stacking and van-der-Waals bonding. It is found that, due to the bonding anisotropy of GeTe and Sb2Te3, the materials intermix to form van-der-Waals heterostructures of Sb2Te3 and stable GeSbTe. Moreover, it is found through annealing experiments that intermixing is stronger for higher temperatures. The resulting ground state structure contradicts the dominant ab-initio results in the literature, requiring revisions of the proposed switching mechanisms. Overall, these findings shed light on the bonding nature of GeTe–Sb2Te3 superlattices and open a way to the understanding of their functionality.
We studied GeTe structures in superlattice phase change memories (superlattice PCMs) with a [GeTe/Sb2Te3] stacked structure by X-ray diffraction (XRD) analysis. We examined the electrical characteristics of superlattice PCMs with films deposited at different temperatures. It was found that XRD spectra differed between the films deposited at 200 °C and 240 °C; the differences corresponded to the differences in the GeTe sequences in the films. We applied first-principles calculations to calculate the total energy of three different GeTe sequences. The results showed the Ge-Te-Ge-Te sequence had the lowest total energy of the three and it was found that with this sequence the superlattice PCMs did not run.
The resistance of amorphous chalcogenides used in phase change memory devices increases over time due to structural relaxation (SR). The resistance drift usually follows a power law with time described by an exponent nu. Understanding the origin of may lead to engineering methods to improve the stability in memory devices. This work presents an analytical model to describe the activation energies for conduction and SR based on the Meyer-Neldel rule. The model accounts for the observed temperature and time dependence of resistance, and highlights that nuis related to the ratio between conduction and SR activation energies at any given time during drift.
The XPS/XAES technique is applied to analyze the dominant electronic state of In, Ga, Ge impurities in PbTe single crystals doped above the point of Fermi level stabilization. It is shown that the effective electronic state of In impurity in PbTe can be represented as a mixture of 5s25p1 and 5s05p3 configurations, while Ga impurity atoms are present in the donor configuration 4s04p3. Oxidation state of Ge-atom is more than 2+. Vacancionic and interstitial clusters were revealed in Pb1-xInxTe by x-ray diffusive scattering method.
The energies of Ge 2p3/2, Ge 3d, Te 3d5/2, Te 4d5/2 and Sn 3d5/2 photopeaks were measured for vacuum-cleaved GeTe and Ge0.9Sn0.1Te crystals, obtained by the ‘vapour–solid liquid’ technique (VLS). The oxidation of cleaved surfaces in air at ambient temperature and humidity was studied by X-ray photoelectron spectroscopy (XPS). The oxidation seems to take place even after few minutes of air exposure. The first stage of the oxidation results in entire Ge oxidation to the oxidation state 4+ and partial Te oxidation to the elemental state. The intermediate oxidation product is supposed to be GeO2−xTex. The second stage is slower than the first one, and it leads to further Te oxidation to 4+ oxidation state and also the significant surface enrichment in Ge.
A rapid and reversible transition between a highly resistive and conductive state effected by an electric field, which we have observed in various types of disordered semiconducting material, is described in detail. The switching parameters and chemical composition of a typical material are presented, and microscopic mechanisms for the conduction phenomena are suggested.
Core-level and valence-band spectra have been obtained by means of x-ray photoemission spectroscopy for the group IV, V, and VI elements Ge, Sn, Pb, As, Sb, Bi, S, Se, and Te and the group IV-VI compounds GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbS, PbSe, and PbTe. These results, taken under ultrahigh-vacuum conditions with unmonochromatized x rays, are presented and discussed in terms of the bonding in materials with an average valence of 5. The effects of relaxation on the chemical shifts are found to be relatively small. The chemical shifts are found to vary in a manner similar to that expected from the magnitude of the elemental electronegativities except for the ordering of the shifts of GeS and GeSe. Relative charge transfers are calculated from the chemical shifts and are found to be in general agreement with ionicities calculated using the Phillips-Van Vechten theory although there is some disagreement as to their magnitudes. A consideration of the structures of the compounds relative to the charge transfers demonstrates the importance of metallic as well as covalent and ionic bonding in determining the most stable structure. The value of critical ionicity carried over from the average-valence-4 materials does not apply to the average-valence-5 materials and this concept does not appear useful in understanding their bonding because of the increased importance of nondirectional metallic bonding.
An approach for electronic structure calculations is described that generalizes both the pseudopotential method and the linear augmented-plane-wave (LAPW) method in a natural way. The method allows high-quality first-principles molecular-dynamics calculations to be performed using the original fictitious Lagrangian approach of Car and Parrinello. Like the LAPW method it can be used to treat first-row and transition-metal elements with affordable effort and provides access to the full wave function. The augmentation procedure is generalized in that partial-wave expansions are not determined by the value and the derivative of the envelope function at some muffin-tin radius, but rather by the overlap with localized projector functions. The pseudopotential approach based on generalized separable pseudopotentials can be regained by a simple approximation.
We present ab initio quantum-mechanical molecular-dynamics calculations based on the calculation of the electronic ground state and of the Hellmann-Feynman forces in the local-density approximation at each molecular-dynamics step. This is possible using conjugate-gradient techniques for energy minimization, and predicting the wave functions for new ionic positions using subspace alignment. This approach avoids the instabilities inherent in quantum-mechanical molecular-dynamics calculations for metals based on the use of a fictitious Newtonian dynamics for the electronic degrees of freedom. This method gives perfect control of the adiabaticity and allows us to perform simulations over several picoseconds.