Interfacial Phase Change Memory Research Articles

Comprehensive study of the ultrafast photoexcited carrier dynamics in Sb2Te3–GeTe superlattices

Abstract Chalcogenide superlattices Sb2Te3-GeTe is a candidate for interfacial phase-change memory (iPCM) data storage devices. By employing terahertz emission spectroscopy and the transient reflectance spectroscopy together, we investigate the ultrafast photoexcited carrier dynamics and current transients in Sb2Te3-GeTe superlattices. Sample orientation and excitation polarization dependences of the THz emission confirm that ultrafast thermo-electric, shift and injection currents contribute to the THz generation in Sb2Te3-GeTe superlattices. By decreasing the thickness and increasing the number of GeTe and Sb2Te3 layer, the interlayer coupling can be enhanced, which significantly reduces the contribution from circular photo-galvanic effect (CPGE). A photo-induced bleaching in the transient reflectance spectroscopy probed in the range of ~1100 nm to ~1400 nm further demonstrates a gapped state resulting from the interlayer coupling. These demonstrates play an important role in the development of iPCM-based high-speed optoelectronic devices.

Advanced interfacial phase change material: Structurally confined and interfacially extended superlattice

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.

Phase change in GeTe/Sb2Te3 superlattices: Formation of the vacancy-ordered metastable cubic structure via Ge migration

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.

(Digital Presentation) Electrothermal Modeling of Interfacial Phase Change Memory

Phase change memory (PCM) is a high-speed non-volatile memory that utilizes the reversible and fast transition between highly conductive crystalline phase and highly resistive (dielectric) amorphous phase of the phase change material to store information and the large electrical resistivity contrast between the two phases for retrieval of the stored data [1,2]. One of the main challenges for PCM is the large power required to heat the active region above crystallization or melting temperature. Lower energy and higher speed operations have been demonstrated with thin film superlattice stacks of phase change materials known as interfacial phase change memory (iPCM) [3-6]. The mechanisms behind the improved performance of iPCM are still under investigation but recent work indicates similar crystallization and melt-quench operation of these devices [5].In this work, we perform electrothermal finite element simulations of reset and set operations on iPCM structures consisting of alternately stacked Ge2Sb2Te5 (GST) and GeTe layers using COMSOL multiphysics [7-10]. Electrical pulses are applied for reset and set processes utilizing an internal circuit model where a transistor is used as an access device. Coupled electric current and heat transfer physics are employed to incorporate Joule heating and thermoelectric effects (Thomson heat within a single material and Peltier heat at material interfaces) with temperature dependent Seebeck coefficients, thermal conductivities, electrical resistivities, heat capacities and thermal boundary resistances (TBR) for each material / material pairs. Latent heat of fusion is included in the amorphous-crystalline and solid-liquid transitions [10], giving rise to heat release at the crystal-amorphous boundaries during crystal growth and heat absorption at the grain boundaries during amorphization. Grain boundaries and material interfaces have high energy sites, making them easier to melt, described as heterogeneous melting [10].iPCM [5] structures utilize engineered interfaces formed between nanometer scale thin-film stacks, promoting amorphization through increased number of material interfaces and reduced thermal conduction due to TBR. Furthermore, the melting temperature, electrical conductivity and Seebeck coefficient of the different materials within an iPCM device differ. Hence, such layered structures may have the advantage of melting of only one of the alternating layers assisted by local heating or cooling due to Peltier effect at the interfaces.Our results on iPCM and conventional PCM structures of same dimensions and geometry (20 nm wide, 150 nm high pore-cells) show ~ 50% reduction in reset times and more consistent set times for iPCM cells due to lesser variations in grain sizes and location of boundaries.Acknowledgment: This work is partially supported by the National Science Foundation under award DMR-1710468.

Internal reverse-biased p–n junctions: A possible origin of the high resistance in chalcogenide superlattice for interfacial phase change memory

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.

Bidirectional Electric-Induced Conductance Based on GeTe/Sb2Te3 Interfacial Phase Change Memory for Neuro-Inspired Computing

Corresponding to the principles of biological synapses, an essential prerequisite for hardware neural networks using electronics devices is the continuous regulation of conductance. We implemented artificial synaptic characteristics in a (GeTe/Sb2Te3)16 iPCM with a superlattice structure under optimized identical pulse trains. By atomically controlling the Ge switch in the phase transition that appears in the GeTe/Sb2Te3 superlattice structure, multiple conductance states were implemented by applying the appropriate electrical pulses. Furthermore, we found that the bidirectional switching behavior of a (GeTe/Sb2Te3)16 iPCM can achieve a desired resistance level by using the pulse width. Therefore, we fabricated a Ge2Sb2Te5 PCM and designed a pulse scheme, which was based on the phase transition mechanism, to compare to the (GeTe/Sb2Te3)16 iPCM. We also designed an identical pulse scheme that implements both linear and symmetrical LTP and LTD, based on the iPCM mechanism. As a result, the (GeTe/Sb2Te3)16 iPCM showed relatively excellent synaptic characteristics by implementing a gradual conductance modulation, a nonlinearity value of 0.32, and 40 LTP/LTD conductance states by using identical pulse trains. Our results demonstrate the general applicability of the artificial synaptic device for potential use in neuro-inspired computing and next-generation, non-volatile memory.

Sputter‐grown GeTe/Sb 2 Te 3 superlattice interfacial phase change memory for low power and multi‐level‐cell operation

The multi-level feature of GeTe/Sb2Te3 interfacial phase change memory was achieved by applying a designed voltage-based pulse. It stably demonstrated five multi-level states without interference for 90 cycles by varying the pulse width. GeTe/Sb2Te3 interfacial phase change memory demonstrated retention time of > 1.0 × 103 s, presenting the significantly low drift coefficient (ν) of < 0.009, indicating no resistivity drift due to the structure relaxation of glass. In addition, the reset energy consumption of GeTe/Sb2Te3 interfacial phase change memory was reduced by more than 85% compared to conventional Ge2Sb2Te5 phase change memory at each bottom electrode contact size. Multi-level-cell operation mechanism and gradual increase in conductance value of GeTe/Sb2Te3 interfacial phase change memory was explained by a partial resistance transition model where phase transition occurred partially in all layers. The result of the GeTe/Sb2Te3 interfacial phase change memory performance is expected to bring great advantages to the next-generation storage class memory industry that requires low energy and high density.

RETRACTED: Kang et al. Achievement of Gradual Conductance Characteristics Based on Interfacial Phase-Change Memory for Artificial Synapse Applications. Electronics 2020, 9, 1268

The authors and journal retract the article, “Achievement of Gradual Conductance Characteristics Based on Interfacial Phase-Change Memory for Artificial Synapse Applications” [...]

Time-Domain Thermoreflectance Study on Superlattice-like Phase Changing Chalcogenide Materials

Phase change memory (PCM) has been developed as one of the next generation memory candidates due to its high read/write speeds, high densities, and non-volatile characteristics. This memory uses the phase change of the chalcogenide materials by Joule heating. However, there is a problem of requesting high reset current, thereby increasing power consumption during melt-quench process for its amorphization. As a way to solve the high reset current, interfacial PCM (iPCM) was suggested. It is based on the metastable states formed in superlattice-like GeTe/Sb2Te3 stack of high quality. This PCM operates with a reversible structural change between high and low resistance states without melt-quench process. However, if the heating from electrode is too excessive during the iPCM operation process, unwanted melting can occur and iPCM characteristics can be lost. Therefore, it is necessary to study the thermal effects of superlattice-like phase change material and electrode in order to ensure stability in conventional PCM or iPCM operation.In this study, we conduct time-domain thermoreflectance study on the molecular-beam-epitaxially grown phase change materials; GeTe and Sb2Te3. Phase change layer was consisted of single or superlattice-like structure. TiN metal layer was used to see the thermal boundary resistance between the metal and phase change materials. Au metal layer was deposited as a photothermal transducer layer due to its stability and thermoreflectance coefficient value. Thermal conductivities of signle and superlattice-like thin films are compared to analyze the thermal effects. In addtion, heat conduction between the metallic TiN and phase change material of high quality is considered.

Electric Fields and Interfacial Phase‐Change Memory Structures

Phase‐change memory (PCM), a nonvolatile electrical memory based upon the local structure of chalcogenide compounds such as , is playing an ever increasing role in society. In PCM, information is stored via structure, specifically crystalline or amorphous phases. As generation of the amorphous state requires a melt‐quench process, the energy required for switching is relatively large. Interfacial PCM (iPCM) is a form of PCM that greatly improves energy efficiency consisting of a short‐period superlattice. Unlike conventional PCM, iPCM is believed to switch between two crystalline states. The large energy reduction to switch iPCM and the absence of a melt‐quenched phase has led to speculation that electrical fields may play a role in the switching process. Herein, ab initio molecular dynamics is employed to explore electric field effects on proposed iPCM structures. Structures are terminated by van der Waals (vdW)‐bonded layers to avoid dangling bonds. Unlike previous speculation in the literature, the effect of electrical fields on Ge atoms is minimal with Te–Te vdW gaps experiencing the largest change. The electric‐field‐induced rearrangements vary; however, for all structures, a dilation in the vdW gap is observed possibly facilitating the proposed switching mechanisms.

Chalcogenide Materials Engineering for Phase‐Change Memory and Future Electronics Applications: From Sb–Te to Bi–Te

Chalcogenide materials play essential roles in modern nonvolatile memory technology in the form of both phase‐change memory (PCM) and selector devices. Herein, Bi–Te binary alloys are explored as an alternative candidate for superlattice (SL) or interfacial PCM (iPCM). GeTe/Bi4Te3 (GT/BT) SL exhibits similar structural features to conventional GeTe/Sb2Te3 (GT/ST) SL, such as highly oriented crystal grains and intermixing. Furthermore, preliminary device measurements show that Ge–Bi–Te (GBT) SL switches in a similar manner to conventional Ge–Sb–Te (GST), suggesting that they may be a promising candidate for memory applications. In addition, Bi2Te3/Sb2Te3 (BT/ST) heterostructure films have been successfully fabricated and show clear interface stacking at the atomic level. Although the BT/ST heterostructure is ostensibly a p–n junction, rectifying behavior is not observed in current (I)–voltage (V) measurements due to the existence of a large number of carriers in both layers. Finally, density functional theory (DFT)‐based simulations suggest that an ideal BT/ST heterostructure may possess intriguing topological properties that can enable novel functional devices. The Bi–Te binary alloys offer promising potential for optimizing PCM performance as well as for the realization of novel functional electronic devices.

Temperature dependent evolution of local structure in chalcogenide-based superlattices

Interfacial phase change memory utilizing chalcogenide-based superlattices (CSLs) offers outstanding device performance and is an emerging contender to replace conventional phase change memory based on single layer materials. In this work, evolution of local structure in epitaxial GeTe/Sb2Te3 based superlattices grown on Si(111) substrates at different growing temperatures by pulsed laser deposition (PLD) is studied by a combination of atomic-resolution scanning transmission electron microscopy with energy dispersive X-ray spectroscopy (EDX). Experimental results show the formation of single Ge-rich Ge-Sb-Te units intercalated with Sb2Te3 building units at low deposition temperatures (100–120 °C). However, the growth of thermodynamically stable layered Ge-Sb-Te crystal structures is observed at high growing temperatures (185–200 °C), while layered GeSb2Te4 thin film is formed at a deposition temperature of 220 °C. Atomic-resolution EDX analysis revealed disordered Ge/Sb cation layers within of Ge-Sb-Te building units. Overall, this work demonstrates that the formation of layered Ge-Sb-Te structures is thermodynamically driven process. It cannot be suppressed at high growing temperatures, regardless of deposition technique. However, diffusivity of Ge and Sb atoms can be largely restricted at low deposition temperatures. This opens a way to further optimize the microstructure of CSLs.

RETRACTED: Achievement of Gradual Conductance Characteristics Based on Interfacial Phase-Change Memory for Artificial Synapse Applications

In this paper, gradual and symmetrical long-term potentiation (LTP) and long-term depression (LTD) were achieved by applying the optimal electrical pulse condition of the interfacial phase-change memory (iPCM) based on a superlattice (SL) structure fabricated by stacking GeTe/Sb2Te3 alternately to implement an artificial synapse in neuromorphic computing. Furthermore, conventional phase-change random access memory (PCRAM) based on a Ge–Sb–Te (GST) alloy with an identical bottom electrode contact size was fabricated to compare the electrical characteristics. The results showed a reduction in the reset energy consumption of the GeTe/Sb2Te3 (GT/ST) iPCM by more than 69% of the GST alloy for each bottom electrode contact size. Additionally, the GT/ST iPCM achieved gradual conductance tuning and 90.6% symmetry between LTP and LTD with a relatively unsophisticated pulse scheme. Based on the above results, GT/ST iPCM is anticipated to be exploitable as a synaptic device used for brain-inspired computing and to be utilized for next-generation non-volatile memory.

Local structure of [(GeTe)2/(Sb2Te3)m]n super-lattices by x-ray absorption spectroscopy

Herein, the local structure of [(GeTe)2/(Sb2Te3)m]n chalcogenide super-lattices (SLs), which are at the basis of emerging interfacial Phase-Change Memory (iPCM), is studied by x-ray absoprtion spectroscopy at the Ge-K edge. The quantitative analysis of the first coordination shells reveals that the SLs possess a structure very similar to that of thin film of the canonical Ge2Sb2Te5 (GST225) phase-change alloy. By comparing experimental data with ab initio molecular dynamics simulations of the extended x-ray absorption fine structure spectra, we show that chemical disorder is mandatory in order to reproduce the experimental data in the full spectral range. As a result, we can unambiguously conclude that Ge/Sb intermixing resulting from inter-diffusion of the GeTe and Sb2Te3 layers within SLs is inherent to SLs and is not induced by sample preparation method nor by interaction with the electron beam of electron microscopes used in all the previous studies that were suggesting such a phenomenon. We further evidence that the short Ge-Te distance is the same in GeTe and GST225 films, as well as in SLs. The main difference is the impact of disorder in GST225 and SLs. Intermixing being definitively present in [(GeTe)2/(Sb2Te3)m]n SLs, this parameter must be considered in future models aiming at going further in the understanding and the development of iPCM technology. This seems mandatory in order to allow such technology to emerge in the near future on the non-volatile memory market.

Effects of electric and magnetic fields on the resistive switching operation of iPCM

Interfacial phase change memory devices based on chalcogenide superlattices show a remarkable performance improvement over traditional phase change memory devices. Here, we report on the effects of the resistive switching of Ge–Te/Sb–Te superlattices in the presence of an external magnetic field at elevated temperature. In addition to the unique thermal dependence of the switching behavior, a new resistance level was found. This resistance level, once initiated, could be then obtained without a magnetic field. The observed phenomena are associated with the structural reconfiguration of domains at the superlattice interfaces and grain boundaries. It has been proposed that these effects may be caused by the localization of spin-polarized electrons generated by a combination of electric and magnetic fields in the ferroelectric phase of the superlattice.

Role of substrate temperature and tellurium flux on the electrical and optical properties of MBE grown GeTe and Sb2Te3 thin films on GaAs (100)

Van der Waals layered GeTe/Sb2Te3 chalcogenide superlattices have demonstrated outstanding performance for use in dynamic resistive memories in what is known as interfacial phase change memory devices due to their low power requirement and fast switching. These devices are made from the periodic stacking of nanometer thick crystalline layers of chalcogenide phase change materials. The mechanism for this transition is still debated, though it varies from that of traditional phase change melt-quench transition observed in singular layers of GeTe and Sb2Te3. In order to better understand the mechanism and behavior of this transition, a thorough study on each constituent layer and the parameters for growth via molecular beam epitaxy was performed. In this work, the authors show the effect of tellurium overpressure and substrate temperature on the growth of thin film GeTe and Sb2Te3 on (100) GaAs. The authors demonstrate the significant role during growth that tellurium overpressure plays in the transport properties of both GeTe and Sb2Te3, as well as the negligible impact this has on both the structural and optical properties. The highest mobility recorded was 466 cm2/V s with a p-type bulk carrier concentration of 1.5 × 1019 cm−3 in Sb2Te3. For GeTe, the highest achieved was 55 cm2/V s at a p-type bulk carrier concentration of 8.6 × 1020 cm−3. The authors discuss transport properties, orientation, and crystal structure and the parameters needed to achieve high mobility chalcogenide thin films.

Growth mechanism of highly oriented layered Sb2Te3 thin films on various materials

Sb2Te3 is a layered material with outstanding properties leading to applications in interfacial phase-change memories, spintronic and thermoelectric devices. For successful integration in devices, controlling the orientation of the atomic planes of Sb2Te3 deposited by sputtering on various materials used for electrodes and on dielectric layers is required. We have succeeded in depositing Sb2Te3 thin films (thickness in the range 10–100 nm) by sputtering in industrial deposition equipments on WSi, TiN, amorphous Si as well as on native and thermal silicon oxide layers. The structure and orientation of the films were studied by x-ray diffraction. The Sb and Te planes are found parallel to the substrate, whatever the nature of the bottom material, provided that the sputtering conditions avoid a Te deficiency in the deposited film. These results show that deposition of Sb2Te3 with out-of-plane orientation on silicon oxide is actually possible, in contrast with previous literature results. Scanning transmission electron microscopy images of the interface between the Sb2Te3 film and the bottom material allow to elucidate the growth mechanism. The formation of a surface layer containing a few Te planes on top of the bottom material is mandatory for the subsequent growth of an out-of-plane oriented Sb2Te3 film by van der Waals epitaxy.

A first-principles study of the switching mechanism in GeTe/InSbTe superlattices.

Interfacial Phase Change Memories (iPCMs) based on (GeTe)2/Sb2Te3 superlattices have been proposed as an alternative candidate to conventional PCMs for the realization of memory devices with superior switching properties. The switching mechanism was proposed to involve a crystalline-to-crystalline structural transition associated with a rearrangement of the stacking sequence of the GeTe bilayers. Density functional theory (DFT) calculations showed that such rearrangement could be achieved by means of a two-step process with an activation barrier for the flipping of Ge and Te atoms which is sensitive to the biaxial strain acting on GeTe bilayers. Within this picture, strain-engineering of GeTe bilayers in the GeTe–chalcogenide superlattice can be exploited to further improve the iPCM switching performance. In this work, we study GeTe–InSbTe superlattices with different compositions by means of DFT, aiming at exploiting the large mismatch (3.8%) in the in-plane lattice parameter between GeTe and In3SbTe2 to reduce the activation barrier for the switching with respect to the (GeTe)2–Sb2Te3 superlattice.

Understanding the switching mechanism of interfacial phase change memory

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.

The underlying physics of interfacial phase change memory

A new article looks at how the switching mechanism works in interfacial phase change memory, an emerging technology with advantages over current memory standards.