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Carbon-doped Ge2Sb2Te5 (CGST) is a potential candidate in phase change random access memory (PCRAM) with superb thermal stability and ultrahigh cycle endurance. Direct observation of the microstructure evolution of CGST is desirable to uncover the phase transformation mechanism on the relationship of nucleation/crystalline behaviors of the crystalline phase at elevated temperatures and the pristine amorphous phase at room temperature. Here, we investigate the structural evolution of CGST using combined in situ techniques. Our in situ x-ray diffraction and ellipsometry results demonstrate that CGST exhibits a much higher phase transition temperature than undoped one. Temperature-dependent in situ transmission electron microscopy observations further reveal that carbon doping plays a critical role in tailoring the properties of GST by tuning the stochasticity of nucleation/crystallization, stabilizing amorphous and crystalline GST via isolating and refining the grain size at room temperature and elevated temperature. Our work provides detailed information for understanding the microscopic origin of crystallization kinetics of carbon-doped phase change materials toward high-performance PCRAM. [ABSTRACT FROM AUTHOR]

Ge 2 Sb 2 Te 5 (GST), a phase change material, generally exhibits two-step crystallization (amorphous → fcc → hcp) to store and process data. The present study reports the crystallization behavior and bonding mechanism of Ga-doped GST thin films with thermal annealing. Ga doping results in the formation of Ga–Te bonds and shows no bonding with other host elements (Ge and Sb), which changes the bonding mechanism and leads to one-step crystallization (amorphous → fcc). The optical transmission contrast confirmed the thermal stabilization of the fcc phase with thermal annealing. These findings suggest that Ga doping into GST thin films has thermally stabilized the metastable fcc phase and suppressed the hcp phase, hence posing it as a potential candidate for phase change memory applications with fast processing speed and low power consumption. [ABSTRACT FROM AUTHOR]

The coupling of ferroelectric, photoelectric, semiconducting, and phase transition properties make two-dimensional (2D) In2Se3 a material platform with great application potential in the phase change memory, intelligent sensing, and in-memory computing devices. However, at present, there are unclear phase transition mechanisms and ferroelectric dynamics in 2D In2Se3, which seriously hinder the development of device applications. In this review, we mainly highlight the phase transition mechanisms and ferroelectric devices of In2Se3 beginning with the history of bulk In2Se3 and of 2D In2Se3. The phase transition relations of the four In2Se3 phases, including α-, β-, β′-, and γ-phases, under various driving forces, are summarized. The different driving forces, including temperature, laser, electric-field, vacancy, doping, and strain, are introduced and discussed. Moreover, the phase-control growth of 2D In2Se3 films and their novel ferroelectric device applications are demonstrated. Finally, a perspective on future research directions of 2D In2Se3 is provided. [ABSTRACT FROM AUTHOR]

The coupling of ferroelectric, photoelectric, semiconducting, and phase transition properties make two-dimensional (2D) In2Se3 a material platform with great application potential in the phase change memory, intelligent sensing, and in-memory computing devices. However, at present, there are unclear phase transition mechanisms and ferroelectric dynamics in 2D In2Se3, which seriously hinder the development of device applications. In this review, we mainly highlight the phase transition mechanisms and ferroelectric devices of In2Se3 beginning with the history of bulk In2Se3 and of 2D In2Se3. The phase transition relations of the four In2Se3 phases, including α-, β-, β′-, and γ-phases, under various driving forces, are summarized. The different driving forces, including temperature, laser, electric-field, vacancy, doping, and strain, are introduced and discussed. Moreover, the phase-control growth of 2D In2Se3 films and their novel ferroelectric device applications are demonstrated. Finally, a perspective on future research directions of 2D In2Se3 is provided. [ABSTRACT FROM AUTHOR]

The dielectric function evolution and electronic bandgap manipulation by silicon (Si) doping for Sb 2 Te 3 phase change films have been investigated by temperature dependent spectroscopic ellipsometry measurements. During the phase change from amorphous to rhombohedral structures, the significant contrast of electronic band structure for pure Sb 2 Te 3 and Si-doped Sb 2 Te 3 (SST) films as functions of temperature (210–620 K) and Si concentration (0%–12%) has been systematically studied by analyzing the dielectric functions, Tauc gap energy, and partial spectral weight integral. The distinct differences can be mainly attributed to the increment of structure order degree, originated from the change of local bonding arrangement. Based upon the evolutions of Tauc gap energy and partial spectral weight integral with increasing temperature for all four samples, it can be concluded that Si doping can inhibit the crystallization of amorphous films and accelerate the phase change process by serving as nanoscale heaters, which is helpful in improving the thermal stability of amorphous films. The elevated crystallization temperature and phase change rate by Si doping contribute to the dependability and endurance for SST-based phase change memory. The present data provide an important direction on the physical mechanism investigation of Si doping Sb 2 Te 3 by optical techniques. [ABSTRACT FROM AUTHOR]

The magnetostructural phase transition in Fe50Al50 alloy with chemically ordered paramagnetic B2 and disordered ferromagnetic (FM) A2 phase has applications in spintronics such as phase-change magnetic memory and magnonic devices. We first conducted a systematic first-principles density functional theory study of the A2 and B2 phases in the Fe50Al50 alloy. A theoretical understanding of this equiatomic alloy's electronic and spin-dynamical properties leads us to the experimental exploration of the FM A2 phase. Therefore, we deposit the 50 nm Fe50Al50 alloy thin film using sputtering and investigate the influence of the Ta buffer layer on its structural and magnetic properties. Our results reveal that the film with a buffer layer exhibits the A2 phase with appreciably higher saturation magnetization (848 emu/cc) than the film without a buffer layer (576 emu/cc). However, the surface roughness and Gilbert damping (α) slightly increase with the presence of the buffer layer from 0.41 to 0.56 nm and 4.35 × 10−3–4.94 × 10−3, respectively. The enhancement in α is due to extrinsic contributions induced by surface inhomogeneities. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Operation speed, data retention, thickness variation, and resistance drift are main shortages for conventional Ge2Sb2Te5 based phase change memory (PCM). In this Letter, we propose a type of ultrathin amorphous carbon (a-C)/Sb2Te multilayer nanostructures with semiconductor process compatibility, which has high speed and excellent reliability in terms of data retention (131 °C for 10-year), thickness variation (1.52%), and resistance drift (0.0095). The PCM devices based on [a-C (1 nm)/Sb2Te (7 nm)]5 multilayer nanostructures exhibit a fast operation speed of 5 ns. The SET/RESET resistance ratio remains constant over 105 cycles by more than two orders of magnitude. The excellent performance of a-C/Sb2Te multilayer nanostructures makes it a promising storage medium to expand the applications of PCM, such as automotive electronics. [ABSTRACT FROM AUTHOR]

Research works on phase change random access memory (PCRAM) based on Ge–Sb–Te (GST) phase change materials have achieved exciting progress, but the industrialization of PCRAM still faces big challenges, including unsatisfied endurance property or unexpected cell structure failure during fabrication. Here, we investigate the impact of the thermal budget in back-end-of-line (BEOL) process on the microstructure evolution of carbon doped GST (CGST) cells. We demonstrate that the as-deposited amorphous CGST in the confined memory cell will transform to face centered-cubic (FCC) phase with uniform grain size during high temperature up to 400 °C in the BEOL process. However, if there is much more unexpected thermal budget during the BEOL process, the FCC-CGST grains will further grow and transform to highly ⟨0001⟩ oriented single crystalline hexagonal (HEX) GST, together with the formation of voids, leading to the structure failure of the storage cells. By virtue of the advanced spherical aberration corrected transmission electron microscopy (Cs-TEM), we find that there are randomly stacked seven-layered and nine-layered atomic arrangements in single crystalline HEX-GST, corresponding to the chemical stoichiometry of Ge2Sb2Te5 and Ge1Sb2Te4, respectively. Interestingly, twin crystal with the coexistence of vacancy-ordered FCC-GST and HEX-GST on the different twin boundary is observed, indicating that the twin crystals play a critical role in the coalescence and the growth of FCC-GST. This work not only sheds light on the structure failure mechanism of GST cell but also provided additional insight into the formation of HEX-phase in a confined GST memory cell. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Ge-rich GeSbTe alloys allowed overcoming temperature limitations of phase-change memory technology. In this paper, we present a thorough investigation of the structural evolution and the crystallization process of these alloys as a function of increasing temperature in annealing. We highlight the progressive rearrangement of the structure toward the demixing of Ge and GeSbTe phases. In particular, we show the stability of Sb–Te units and the development of Ge–Te bonds around these features. We observe the formation of a transient GeSbTe phase, which is driven by crystallization phenomena, leading to a gradual diffusion and expulsion of Ge. Therefore, the system moves toward the complete separation of Ge and Ge2Sb2Te5 stable phases. Furthermore, we investigate the effect of N-doping in Ge-rich GeSbTe, which induces the formation of Ge–N bonds. Such features are demonstrated to be responsible for a delayed structural reorganization to higher temperatures, thus affecting the entire process of crystallization and phase separation in the alloy. [ABSTRACT FROM AUTHOR]

Cu2GeTe3 (CGT) is a promising phase change material for phase change random access memory (PCRAM) applications because of its high thermal stability in the amorphous phase and its capability to undergo rapid phase change. In this paper, the electrical conduction mechanism of a CGT memory device fabricated using W electrodes (W/CGT) was investigated using current–voltage (I–V) measurements and angle resolved hard x-ray photoelectron spectroscopy (AR-HAXPES). The I–V characteristics of the W/CGT memory device were found to display non-linear behavior in the RESET (amorphous) state, while linear behavior was observed in the SET (crystalline) state, indicating that the W/CGT memory device exhibited Schottky conduction in the RESET state, but Ohmic conduction in the SET state. The effective Schottky barrier height was found to increase linearly as the ideality factor decreased to unity with the ideal W/CGT Schottky barrier height in the RESET state estimated to be 0.33 eV, a value in good agreement with the directly measured Schottky barrier height of 0.35 eV between W and amorphous CGT by AR-HAXPES measurements. These results suggest that the interface between the metal electrode and the phase change material plays an important role in PCRAM devices, and its comprehensive understanding is necessary for future application development. [ABSTRACT FROM AUTHOR]

Phase change memory (PCM) is considered as a leading candidate for next generation data storage as well as emerging computing device, but the advancement has been hampered by high switching energy due to the melting process and amorphous relaxation induced large resistance drift. Polymorphic crystal-crystal transition without amorphization in metal dichalcogenides (TMDs) could be employed to solve these issues. Yet, the mechanism is still controversy. A melting-free PCM made of two dimensional (2D) MoTe2, which exhibits unipolar resistive switching (RS) and multi-level states with substantially reduced resistance drift via joule heating, is reported in this work. The device is first prepared based on the temperature dependence of Raman spectrum and electrical transport investigations on MoTe2 films. Significantly improved device performances on energy efficiency, switching speed, and memory window are further achieved by electrode size scaling down, indicating the key role of localized heating. Then, device scale transmission electron microscopy images reveal that the resistive switching stems from the transition between semiconducting 2H phase and metallic 1T′ phase. An entropy induced Te vacancies model is proposed to explain the reversible phase change mechanism in the MoTe2 based device. This study paves the way for further development of PCM based on atomically thin 2D TMDs, aiming for high density storage-class memory and high-precision neuromorphic computing. [ABSTRACT FROM AUTHOR]

The crystallization mechanism of In2S3-doped Sb thin films is studied in detail to verify the potential application in phase change memory. Here, we observe directly that two different crystallization behaviors can exist in In–S–Sb thin layers by using aberration-corrected scanning transmission electron microscopy. The difference between Sb53.3(In2S3)46.7 and Sb30.9(In2S3)69.1 materials is induced by phase separation. The crystallization mechanism of the Sb53.3(In2S3)46.7 material is related to the formation of the nanocomposite structure with continuous precipitation of Sb nanocrystals. The crystallization characteristic of the Sb30.9(In2S3)69.1 material originates from the diffusion-driven In–S/In–S–Sb interface formation that acts as a "n–p" heterojunction, thereby resulting in the "depletion layer effect" and decreasing the carrier density to 7.42 × 1020 cm−3 at 280 °C. Sb30.9(In2S3)69.1 shows good bipolar-type resistance switching characteristics as the conventional Ge2Sb2Te5. This work provides clear experimental evidence to deepen the understanding of the crystallization mechanism for indium chalcogenides alloyed with Sb films, contributing to the improved control of the phase change behavior to establish high-performance multi-level nonvolatile memory and neuromorphic synaptic systems. [ABSTRACT FROM AUTHOR]

We measure heterogeneous power dissipation in phase change memory (PCM) films of 11 and 22 nm thin Ge2Sb2Te5 (GST) by scanning Joule expansion microscopy (SJEM), with sub-50nm spatial and ~0.2 K temperature resolution. The heterogeneous Joule and Peltier effects are explained using a finite element analysis (FEA) model with a mixture of hexagonal close-packed and face-centered cubic GST phases. Transfer length method measurements and effective media theory calculations yield the GST resistivity, GST-TiW contact resistivity, and crystal fraction of the GST films at different annealing temperatures. Further comparison of SJEM measurements and FEA modeling also predicts the thermopower of thin GST films. These measurements of nanometer-scale Joule, thermoelectric, and interface effects in PCM films could lead to energy-efficient designs of highly scaled PCM technology. [ABSTRACT FROM AUTHOR]

This review discusses critical aspects of patterning phase change materials (PCMs), including dry etching, wet clean, and encapsulation, as they dictate the reliability and functionality of the phase change random access memory devices. Specifically, alloys of germanium–antimony–tellurium are used as a model system, and the importance of PCM composition control, critical dimension control, high fidelity pattern transfer, and a system level of ambient control to avoid oxidation that can alter the materials' functionality are highlighted. The research findings motivate the development of a state-of-the-art integrated system that combines dry etch, wet clean, and encapsulation into one platform to realize consistent and successful patterning of PCMs for future generations of the memory devices. [ABSTRACT FROM AUTHOR]

We present thermodynamic crystallization and melting models and calculate phase change velocities in Ge2Sb2Te5 based on kinetic and thermodynamic parameters with a focus on the impacts of grain boundary melting. The calculated phase change velocities are strong functions of grain size, with smaller grains beginning to melt at lower temperatures. Phase change velocities are continuous functions of temperature which determine crystallization and melting rates. Hence, set and reset times as well as power and peak current requirements for switching are strong functions of grain size. Grain boundary amorphization can lead to a sufficient increase in cell resistance for small-grain phase change materials even if the whole active region does not completely amorphize. Isolated grains left in the amorphous regions, the quenched-in nuclei, facilitate templated crystal growth and significantly reduce set times for phase change memory cells. We demonstrate the significance of heterogeneous melting through 2-D electrothermal simulations coupled with a dynamic material phase change model. Our results show reset and set times on the order of ∼1 ns for 30 nm wide confined nanocrystalline (7.5 nm–25 nm radius crystals) phase change memory cells. [ABSTRACT FROM AUTHOR]

Phase-change random access memory (PCRAM) is enabled by a large resistance contrast between amorphous and crystalline phases upon reversible switching between the two states. Thus, great efforts have been devoted to identifying potential phase-change materials (PCMs) with large electrical contrast to realize a more accurate reading operation. In contrast, although the truly dominant resistance in a scaled PCRAM cell is contact resistance, less attention has been paid toward the investigation of the contact property between PCMs and electrode metals. This study aims to propose a non-bulk-resistance-dominant PCRAM whose resistance is modulated only by contact. The contact-resistance-dominated PCM exploited here is N-doped Cr2Ge2Te6 (NCrGT), which exhibits almost no electrical resistivity difference between the two phases but exhibits a typical switching behavior involving a three-order-of-magnitude SET/RESET resistance ratio owing to its large contact resistance contrast. The conduction mechanism was discussed on the basis of current–voltage characteristics of the interface between the NCrGT and the W electrode. [ABSTRACT FROM AUTHOR]

ZnxSbyTez thin films are deposited on quartz or glass substrates by the electron beam evaporation technique in an ultra-high vacuum. A prototype phase change memory device using the ZST (ZnxSbyTez) thin film is fabricated. The current-voltage test results of the device show the threshold voltage of ZST531 (Zn5.18Sb3.75Te1.10 at.%) is 2.4 V, which is similar to that of the device based on pure Ge2Sb2Te5. It is shown that the phase-change device with the ZST film is able to perform several reading and writing cycles and the off/on resistance ratio is nearly 10 under pulse voltage. The switching performance of the device is also investigated. Most importantly, the results of the in situ resistance measurements show that the increase of crystallization temperature and the higher 10-year data retention temperature are as high as 300 °C and 191 °C, respectively. This indicates that the ZnxSbyTez material is quite stable, and thus appropriate for use in phase-change memory. [ABSTRACT FROM AUTHOR]

Tungsten (W) doping effects on Ge2Sb2Te5 (GSTW) phase change films with different concentrations (3.2, 7.1, and 10.8%) have been investigated by variable-temperature spectroscopic ellipsometry. The dielectric functions from 210 K to 660 K have been evaluated with the aid of Tauc-Lorentz and Drude dispersion models. The analysis of Tauc gap energy (Eg) and partial spectral weight integral reveal the correlation between optical properties and local structural change. The order degree increment and chemical bond change from covalent to resonant should be responsible for band gap narrowing and electronic transition enhancement during the phase change process. It is found that the elevated crystalline temperature for GSTW can be related to improved disorder degree. Furthermore, the shrinkage of Eg for GSTW should be attributed to the enhanced metallicity compared with undoped GST. [ABSTRACT FROM AUTHOR]

The time-resolved reflectivity measurements were carried out on the interfacial phase change memory (iPCM) materials ([(GeTe)2(Sb2Te3)4]8 and [(GeTe)2(Sb2Te3)1]20) as well as conventional Ge 2Sb2Te5 alloy at room temperature and above the RESET-SET phase transition temperature. In the high-temperature phase, coherent phonons were clearly observed in the iPCM samples while drastic attenuation of coherent phonons was induced in the alloy. This difference strongly suggests the atomic rearrangement during the phase transition in iPCMs is much smaller than that in the alloy. These results are consistent with the unique phase transition model in which a quasi-one-dimensional displacement of Ge atoms occurs for iPCMs and a conventional amorphous-crystalline phase transition takes place for the alloy. [ABSTRACT FROM AUTHOR]

The phase-change behavior and microstructure changes of N-doped Ge3Sb2Te5 [N-GST(3/2/5)] and Ge2Sb2Te5 [GST(2/2/5)] films during the phase transition from an amorphous to a crystalline phase were studied using in situ temperature-dependent sheet resistance measurements, X-ray diffraction, and transmission electron microscopy. The optical band gaps of N-GST(3/2/5) films are higher than that of GST(2/2/5) film in both the amorphous and face-centered-cubic (fcc) phases. Ge nitride formation by X-ray photoelectron spectroscopy analysis increased the optical band gap and suppressed crystalline grain growth, resulting in an increase in the crystallization temperature and resistance in the fcc phase. As a result, the Ge- and N-doped GST(2/2/5) composite films can be considered as a promising material for phase-change memory application because of improved thermal stability and reduced power consumption. [ABSTRACT FROM AUTHOR]

Exothermal resistance measurement reveals that the phase transition of Ge2Sb2Te5 phase change memory (PCM) can take place far below the traditional crystallization temperature. The activation energy of nucleation is no longer a constant and highly dependent on applied electric fields. The field-dependent activation energy becomes much lower with higher applied field. Further, the field-dependent activation energy can be described by an exponential function of the applied fields. These findings provide physical fundamentals for analysis of nucleation switching mechanism of PCM. A switching model has been developed and the simulated current-voltage curve is in good agreement with the experimental measurement. [ABSTRACT FROM AUTHOR]