Phase Change Memory Applications Research Articles

Non-isothermal crystallization kinetics and memory switching properties of Tl-Se-Ge-Sb chalcogenide semiconductor alloy for thermally stable phase change memory applications

Quaternary (Tl20Se70Ge10)0.85Sb0.15 chalcogenide glass was synthesized using melt-quenching and thermal evaporation techniques for bulk and thin film samples, and its amorphous character was confirmed by XRD. Based on different models of non-isothermal crystallization kinetics, the average values of the glass transition and the crystallization activation energies are 121.33 and 82.94 kJ mol−1, respectively. The crystallization mechanism in the examined composition is 2D nucleation growth, according to Avrami exponent Thermal parameters of the studied quaternary glass, like fragility fluctuation free volume reduced glass transition temperature thermal stability and glass formation ability were investigated and indicated that the (Tl20Se70Ge10)0.85Sb0.15 ChG exhibits a good ability of glass formation and thermal stability. The obtained results of the dc electrical conductivity are found to increase with temperature and decrease with film thickness. The electrical conduction activation energy (0.583 ± 0.004 eV) is thickness independent and the predominant conduction mechanism is the hopping of charge carriers in the band tail localized states. The () curves of (Tl20Se70Ge10)0.85Sb0.15 chalcogenide glass film samples were analyzed and shown to be appropriate for a memory switch. The mean value of the threshold voltage decreases exponentially as temperature increases, whereas it increases linearly as film thickness increases. The values of threshold voltage and threshold resistance activation energies are 0.282 ± 0.003 and 0.521 ± 0.004 eV, respectively. The obtained switching characteristics data were discussed in view of the electrothermal model motivated by current channel Joule heating. These findings highlight the suitability of the investigated composition for various optoelectronic applications, such as memory switching devices, optical data storage, phase-change memories and optical fibres sensing devices.

Calorimetric studies of yttrium doped non-conventional phase-change materials for improved performance

Though phase-change materials (PCMs) are regarded as constituent part of next-generation phase-change memory and other unfolding optoelectronic applications, the kinetics study of glass transition and crystallization, significant property in switching remains obscure in high-temperature region. Hence, this paper reports the investigation of glass transition and crystallization kinetics of Te(1-x) (GeSe0.5)Yx (TGSY) chalcogenide glass using differential scanning calorimetry (DSC) at heating rates 5, 10, 15, 20 °C/min. The effect of increasing Y quantity has been described by connecting structural relaxation kinematics during glass transition phenomena and devitrification while crystallization in chalcogenide glasses with their varied physicochemical characteristics. The inclusion of Y causes a discernible rise in the crystallization rate. The system is compatible with a strong glass-forming liquid, according to the Te(1-x) (GeSe0.5) Yx material fragility index. According to the average values of the kinetic exponent factors, there is heterogeneous nucleation for the investigated composition, which is subsequently followed by a two- or three-dimensional crystal growth phenomenon. Different glass stability criteria have been discussed based on the relationship between the characteristic temperatures. The CZW and CLX criteria were found to be inappropriate for discussing glass stability (GS) for the studied compositions based on the heating rate and composition dependencies of all criteria. The CYL criteria of Yuan et al. is the finest and it demonstrates the optimal ability for evaluating the GS, according to the data that was extracted from several GS criteria and their relative change parameters. By adding Y, thermal stability parameter and enthalpy emitted during the transition of glass and crystalline phases have been found to have an inverse relationship. All studied properties can conclude the application of studied material in phase-change material devices.

The role of arsenic in the operation of sulfur-based electrical threshold switches

Arsenic is an essential dopant in conventional silicon-based semiconductors and emerging phase-change memory (PCM), yet the detailed functional mechanism is still lacking in the latter. Here, we fabricate chalcogenide-based ovonic threshold switching (OTS) selectors, which are key units for suppressing sneak currents in 3D PCM arrays, with various As concentrations. We discovered that incorporation of As into GeS brings >100 °C increase in crystallization temperature, remarkably improving the switching repeatability and prolonging the device lifetime. These benefits arise from strengthened As-S bonds and sluggish atomic migration after As incorporation, which reduces the leakage current by more than an order of magnitude and significantly suppresses the operational voltage drift, ultimately enabling a back-end-of-line-compatible OTS selector with >12 MA/cm2 on-current, ~10 ns speed, and a lifetime approaching 1010 cycles after 450 °C annealing. These findings allow the precise performance control of GeSAs-based OTS materials for high-density 3D PCM applications.

Unveiling the structure and electronic characteristics of amorphous GeS for high performance threshold switching

Ovonic threshold switching selectors are widely studied owing to the essential application in high density phase-change memory. Amorphous GeS is proposed as a potential candidate for the excellent performance. However, the knowledge of amorphous GeS is still insufficient up to date. Here, we have studied the structure and electronic characteristics of GeS in the amorphization process, by using ab initio molecular dynamics simulations. The results indicate that the amorphous GeS is mainly made up of Ge–S bonds. The Ge- and S-centered clusters are dominantly in the form of octahedral structures in liquid GeS. During the amorphization process, most of Ge-centered clusters become highly coordinated octahedrons while a small number of Ge-centered clusters change to tetrahedrons, and the S-centered clusters deviate from the octahedral structure gradually. In addition, the large bandgap and the relatively small mid-gap states in amorphous GeS lead to a high switching voltage.

Mechanism of residue formation on Ge-rich germanium antimony tellurium alloys after plasma etching

In phase-change random access memory (PCRAM) applications, the germanium antimony tellurium alloy (GST) is patterned using halogen etching in inductively coupled plasma reactors. This paper focuses on the surface state evolution of an optimized Ge-rich GST material after plasma etching. Four hours after etching, big dome-shaped residues are observed on PCRAM structures. Their number and size increase with the time of air exposure. X-ray photoelectron spectroscopy and energy-dispersive x-ray spectroscopy analyses reveal an important germanium oxidation on the surface with residues. Their formation is then investigated. Complementary analyses highlight that the moisture environment has a catalytic effect on the residue formation. Based on this study, a detailed mechanism responsible for residue formation is proposed.

Multi-level Threshold Switching and Crystallization Characteristics of Nitrogen Alloyed GaSb for Phase Change Memory Application

Multi-level Threshold Switching and Crystallization Characteristics of Nitrogen Alloyed GaSb for Phase Change Memory Application

Van der Waals epitaxy of pulsed laser deposited antimony thin films on lattice-matched and amorphous substrates

Monatomic antimony thin films have recently attracted attention for applications in phase change memory, nanophotonics, and two-dimensional materials. Although some promising results have been reported, the true potential of Sb thin films is still hindered by the scalability issue and the lack of reliable bottom-up production. Here we demonstrate the growth of Sb thin films on a lattice-matching and amorphous substrates using pulsed laser deposition. C-axis out-of-plane textured Sb thin films were successfully deposited on Sb2Te3 and SiO2/Si3N4 substrates. In the case of growth on Sb2Te3, we show that an intermediate phase is formed at the Sb2Te3–Sb interface playing a crucial role in forming a solid coupling and thus maintaining epitaxy leading to the production of high-quality Sb thin films. A 3–4 nm amorphous Sb seed layer was used to induce texture and suitable surface termination for the growth of Sb thin films on amorphous substrates. The deposition parameters were fine-tuned, and the growth was monitored in situ by reflection high energy electron diffraction. Scanning/transmission electron microscopy unveiled the local structure of produced films showing the formation of ꞵ-phase Sb thin films. Our results demonstrate the feasibility to produce very smooth high-quality antimony thin films with uniform coverage, from few layers to large thicknesses, using pulsed laser deposition. We believe the results of our work on scalable and controllable Sb growth have the potential to open up research on phase change materials and optoelectronics research.

Co-doping: An effective strategy for developing stable and high-speed Sb2Te-based phase-change memory

Balancing operation speed and thermal stability is a big challenge in phase change memory (PCM). In this work, a carbon (C) and chromium (Cr) co-doped Sb2Te strategy has been proposed for achieving high operation speed and high stability in PCM applications. In general, doping with the appropriate Cr element is beneficial to improve thermal stability, but it will sacrifice its operation speed. C-doping can enhance thermal stability and retain its fast phase transition properties due to the carbon elements tend to form agglomerates in the host that ameliorate disorder of the amorphous phase without loss of the phase transition rate. Intriguingly, the as-prepared C1.19Cr0.23Sb2Te material exhibits good data retention (T10-year @ 155.0 °C) and low-volume change rate (1.8%), as well as fast switching speed (4 ns) and good endurance (>1 × 105 cycles). This research indicates that C and Cr co-doping is an effective method to achieve excellent stability of phase-change materials without sacrificing the phase-transition rate of Sb2Te materials.

Successive crystallization in indium selenide thin films for multi-level phase-change memory

Increasing the storage density of phase-change memory is a challenging subject towards the universal memory commercialization. Multi-level data storage can be implemented in phase-change memory cells by designing multiple stages of crystallization of phase-change materials, which is favorable to push forward the application of phase-change memory in storage-class memory and the emerging in-memory computing. Here, the structure and properties of In2Se3 phase-change thin films with multi-level phase transitions are investigated. The In2Se3 thin films changes resistance states twice upon heating with high crystallization temperature and good thermal stability. The amorphous In2Se3 thin films undergo partial crystallization of the Se phase followed by crystallization of the γ-In2Se3 phase, with successive stages of crystallization accounting for the three distinct levels of resistivity. The phase-change memory cell based on In2Se3 thin films shows a continuous switching process of high resistance state, intermediate resistance state and low resistance state with low drift coefficient in SET-RESET operations at a speed as fast as 60 ns, and the RESET power is as low as 311 pJ, indicating that the In2Se3 thin films have good performance of three-state storage property and can effectively improve the memory density.

Graphite Carbon-Doped Sb2Te Nanostructures for Phase-Change Memory Applications

High thermal stability, fast operation speed, low thickness variation, and low resistance drift of phase-change nanomaterials are the essential characteristics in phase-change memory (PCM) applications. In this work, we put forward a graphite carbon-doped Sb2Te (C-Sb2Te) chalcogenide with semiconductor process compatibility. Our results prove that the proposed C-Sb2Te has excellent thermal stability and high operation speed. More importantly, the thickness change and resistance drift are only 0.89% and 0.0149, respectively. The C-Sb2Te-based memory device exhibits a high switching speed to the instrument test limit (5 ns) with a large resistance ratio, low operation voltage (2 V), and low power consumption (6.9 pJ). The proposed C-Sb2Te nanostructure material exceeds both conventional Ge2Sb2Te5 and transition-metal-doped Sb2Te materials in terms of its performance. Ab initio molecular dynamics simulations reveal that C–C and C–Sb bonds as well as C–C chains are formed in C-Sb2Te, and C doping constrains phase transition in a small region and refines grains of C-Sb2Te, thus resulting in the high performance. Our study suggests that C-Sb2Te is a potential candidate for high-speed, high-thermal-stability, and high-reliability PCM applications.

GeTe ultrathin film based phase-change memory with extreme thermal stability, fast SET speed, and low RESET power energy

We designed the phase-change memory (PCM) cell based on ultrathin GeTe film (∼10 nm) and homemade nanoscale electrode filling craft to improve data retention ability and reduce programming energy, respectively. It was found that the temperature for ten years’ data retention of this ultrathin GeTe film is 160 ± 32.8 °C, which is much higher than that of conventional Ge2Sb2Te5 (GST, 83 ± 20.6 °C) film. Benefit to the nature of fragile-to-strong crossover behavior in GeTe supercooled liquids that was confined in a two-dimension structure, a fast SET speed of 6 ns is also detected in this ultrathin GeTe PCM. Moreover, the RESET power consumption of this ultrathin GeTe PCM is measured as 1.8 ± 0.5 nJ, and it is much lower than that of GST PCM (16.5 ± 1.5 nJ), which is attributed to the nanoscale electrode of the devices. The above-mentioned improvements enable the application of ultrathin GeTe PCM in neuromorphic computing.

Study on Texture Formation of Sb2Te Thin Films for Phase Change Memory Applications

We investigated the texture formation of Sb2Te thin films for phase change memory applications. The Sb2Te thin films with different thicknesses were deposited on Si (100) wafers by the magnetron sputtering method. As-deposited Sb2Te thin films were annealed at various temperatures and times. The texture characterization was performed by using X-ray diffraction (XRD) and electron backscatter diffraction (EBSD). Experimental results show that the annealed Sb2Te thin films exhibit the 112¯0 and 101¯0 prismatic texture. The formation of prismatic texture is induced by the lattice strain, surface energy, and coarse grains, in which the lattice strain is the essential origin of prismatic preference. Electronic transport properties of Sb2Te thin films were monitored by a physical property measurement system (PPMS). It was found that the formation of prismatic texture promotes the increase of carrier mobility. The stability of the film–substrate interface was also assessed by calculating mismatch. The prismatic-preferred Sb2Te thin films exhibit higher mismatch with a silicon wafer, reducing the interface stability.

Advantages of Ta-Doped Sb3Te1 Materials for Phase Change Memory Applications.

Phase change memory (PCM), a typical representative of new storage technologies, offers significant advantages in terms of capacity and endurance. However, among the research on phase change materials, thermal stability and switching speed performance have always been the direction where breakthroughs are needed. In this research, as a high-speed and good thermal stability material, Ta was proposed to be doped in Sb3Te1 alloy to improve the phase transition performance and electrical properties. The characterization shows that Ta-doped Sb3Te1 can crystallize at temperatures up to 232 °C and devices can operate at speeds of 6 ns and 8 × 104 operation cycles. The reduction of grain size and the density change rate (3.39%) show excellent performances, which are both smaller than that of Ge2Sb2Te5 (GST) and Sb3Te1. These properties conclusively demonstrate that Ta incorporation of Sb3Te1 alloy is a material with better thermal stability and faster crystallization rates for PCM applications.

GeTe/CrSb2Te superlattice-like thin film for excellent thermal stability and high phase change speed

Thermal stability and operation speed are two key challenges in phase change memory (PCM). This work reports GeTe/Cr0.16Sb2Te (GT/CrST) superlattice-like (SLL) films for both high operation speed and superior thermal stability. The thermal properties, phase change behaviors, microstructural evolution and the electrical performances are investigated in detail. Results show that [GT(8 nm)/CrST(2 nm)]7 film possesses excellent ten-year data-retention (T10-year=156 ºC), small density change rate (2.6%), ultrafast reversible phase change (0.5 ns), and low resistance drift coefficient (∼0.07). Furthermore, the [GT(8 nm)/CrST(2 nm)]7 based PCM cell has the reversible operation time of as low as 8 ns and low power consumption of 8.1×10−12 J. The two-dimensional finite element analysis confirms that the lower power consumption is ascribed to the existence of interfacial thermal resistance in SLL thin film, leading to the lower thermal conductivity. Results indicate that [GT(8 nm)/CrST(2 nm)]7 thin film has great potential for PCM application with excellent thermal stability and phase change speed.

Elemental Redistribution During the Crystallization of Ge–Cu–Te Thin Films for Phase-Change Memory

Herein, a GeCu2Te2 alloy is proposed as a phase-change material for application in nonvolatile phase-change random access memory (PRAM). The crystallization kinetics and microchemical changes during phase transformation are investigated, and their correlation with the electrical behaviors of the GeCu2Te2 thin films are examined. The key findings are as follows: (ⅰ) the GeCu2Te2 alloy shows a higher crystallization temperature (∼185 °C) than the classic Ge2Sb2Te5 (GST) thin films, thus demonstrating superior thermal stability; (ⅱ) the crystallization kinetics demonstrate a decreasing in the Avrami exponent n from 4, which is related to the growth-dominated crystallization process evidenced by the micromorphology; (ⅲ) a massive redistribution of the chemical elements along the depth of the thin films during crystallization is considered to be driven by selective surface oxidation at amorphous state, and stress buildup during crystallization. In addition, the crystallization-induced stress is determined as ∼168 MPa by utilizing the wafer curvature and X-ray diffraction methods for the GeCu2Te2 thin films. Finally, the lower threshold switching voltage ∼1.72 V for amorphous GeCu2Te2 thin films is beneficial for reducing the SET operating power consumption. The authors believe that these results are valuable for the optimal phase change material design.

Influence of yttrium element on the crystallization performance of ZnSb alloy for phase change memory application

The crystallization behavior and electrical performance of Y-doped Zn15Sb85 phase change material were proposed and experimental examined. The relationship between the resistance and temperature reveals that the Y dopant is able to enhancing the thermal stability (Tc ~ 237°C, T10 ~ 169 °C) and resistivity (Ra ~ 105 Ω, Rc ~ 102 Ω) of Zn15Sb85 films, which are suitable for automobile design and surface mount technology. XRD results indicate that the Y dopant could effectively inhibit grain growth and reduce grain size. Meanwhile, XPS illustrates that Y is more likely to form bonds with Sb. Further, the resistance drift index and surface roughness become small after doping Y element, which is of great benefit to improving the reliability and electrical performance of the device. Moreover, T-shaped phase change memory cells based on Y0.36(Zn15Sb85)0.64 film were also built and analyzed. The characteristic of current − voltage (I-V) and resistance − voltage (R-V) prove that the SET and RESET operations can be achieved by electric induction, implying the excellent candidate of Y-doped Zn15Sb85 material for high thermal and high reliability application.

Ultra-Stable, Endurable, and Flexible Sb2TexSe3–x Phase Change Devices for Memory Application and Wearable Electronics

Flexible memory and wearable electronics represent an emerging technology, thanks to their reliability, compatibility, and superior performance. Here, an Sb2TexSe3-x (STSe) phase change material was grown on flexible mica, which not only exhibited superior nature in thermal stability for phase change memory application but also revealed novel function performance in wearable electronics, thanks to its excellent mechanical reliability and endurance. The thermal stability of Sb2Te3 was improved obviously with the crystallization temperature elevated 60 K after Se doping, for the enhanced charge localization and stronger bonding energy, which was validated by the Vienna ab initio simulation package calculations. Based on the ultra-stability of STSe, the STSe-based phase change memory shows 65 000 reversible phase change ability. Moreover, the assembled flexible device can show real-time monitoring and recoverability response in sensing human activities in different parts of the body, which proves its effective reusability and potential as wearable electronics. Most importantly, the STSe device presents remarkable working reliability, reflected by excellent endurance over 100 s and long retention over 100 h. These results paved a novel way to utilize STSe phase change materials for flexible memory and wearable electronics with extreme thermal and mechanical stability and brilliant performance.

Evaluation of vibrational properties and local structure change during phase transition in Ge2Sb2Te5 and In3SbTe2 phase change materials

Temperature-dependent local structural details of In3SbTe2 (IST) and Ge2Sb2Te5 (GST) phase change materials are explored with the aid of Raman scattering and x-ray photoelectron spectroscopy (XPS) techniques. Significant temperature-induced changes occur in the local structure of the phase change material, facilitating the amorphous to crystalline phase transformation. These two phases exhibit a large resistivity contrast, which is utilized to store data in the phase change memory application. The Raman spectra recorded for IST material suggest that the as-deposited sample (amorphous phase) first crystallized around 300 annealing temperature with two binary phases InTe and InSb formations. InTe and InSb phases were obtained at ∼85.5 cm−1 and ∼180 cm−1 Raman shift, respectively, having vibration modes associated with B1g symmetry and transversal optical phonons with Г15 symmetry. Further annealing at a higher temperature of 400 , a ternary IST phase is obtained at ∼163 cm−1 Raman shift indicating the transformation to a fully crystalline state. On the other hand, the amorphous GST material forms a metastable face-centred cubic phase and stable hexagonal (HEX) phase upon crystallization. The Raman findings demonstrate the changes in vibration modes of Ge–Te and Sb–Te bonds during phase switching without any phase separation. Crystalline GST (HEX phase) comprises rising peaks of GeTe4 and GeTe4−n Ge n (n = 1, 2) corner-sharing tetrahedra with A1 mode at ∼104.5 cm−1 and ∼137 cm−1 Raman shift, respectively, and a declining Sb2Te3 peak at ∼175 cm−1, having A1g (2) vibration mode. Furthermore, the XPS analysis displays the changes in the bonding mechanism of the elements present in the phase change material during the amorphous to crystalline phase transition, firmly supporting the Raman observations.

Electrical and structural properties of binary Ga–Sb phase change memory alloys

Material properties of Ga–Sb binary alloy thin films deposited under ultra-high vacuum conditions were studied for analog phase change memory (PCM) applications. Crystallization of this alloy was shown to occur in the temperature range of 180–264 °C, with activation energy >2.5 eV depending on the composition. X-ray diffraction (XRD) studies showed phase separation upon crystallization into two phases, Ga-doped A7 antimony and cubic zinc-blende GaSb. Synchrotron in situ XRD analysis revealed that crystallization into the A7 phase is accompanied by Ga out-diffusion from the grains. X-ray absorption fine structure studies of the local structure of these alloys demonstrated a bond length decrease with a stable coordination number of 4 upon amorphous-to-crystalline phase transformation. Mushroom cell structures built with Ga–Sb alloys on ø110 nm TiN heater show a phase change material resistance switching behavior with resistance ratio >100 under electrical pulse measurements. TEM and Energy Dispersive Spectroscopy (EDS) studies of the Ga–Sb cells after ∼100 switching cycles revealed that partial SET or intermediate resistance states are attained by the variation of the grain size of the material as well as the Ga content in the A7 phase. A mechanism for a reversible composition control is proposed for analog cell performance. These results indicate that Te-free Ga–Sb binary alloys are potential candidates for analog PCM applications.

Neuromorphic Photonic Memory Devices Using Ultrafast, Non-Volatile Phase-Change Materials.

The search for ultrafast photonic memory devices is inspired by the ever-increasing number of cloud-computing, supercomputing, and artificial-intelligence applications, together with the unique advantages of signal processing in the optical domain such as high speed, large bandwidth, and low energy consumption. By embracing silicon photonics with chalcogenide phase-change materials (PCMs), non-volatile integrated photonic memory is developed with promising potential in photonic integrated circuits and nanophotonic applications. While conventional PCMs suffer from slow crystallization speed, scandium-doped antimony telluride (SST) has been recently developed for ultrafast phase-change random-access memory applications. An ultrafast non-volatile photonic memory based on an SST thin film with a 2 ns write/erase speed is demonstrated, which is the fastest write/erase speed ever reported in integrated phase-change photonic devices. SST-based photonic memories exhibit multilevel capabilities and good stability at room temperature. By mapping the memory level to the biological synapse weight, an artificial neural network based on photonic memory devices is successfully established for image classification. Additionally, a reflective nanodisplay application using SST with optoelectronic modulation capabilities is demonstrated. Both the optical and electrical changes in SST during the phase transition and the fast-switching speed demonstrate their potential for use in photonic computing, neuromorphic computing, nanophotonics, and optoelectronic applications.