Phase-change random access memory (PCRAM) has attracted much attention for next-generation nonvolatile memory that can replace flash memory and can be used for storage-class memory. Generally, PCRAM relies on the change in the electrical resistance of a phase-change material between high-resistance amorphous (reset) and low-resistance crystalline (set) states. Herein, we present an inverse resistance change PCRAM with CrGeTe (CrGT) that shows a high-resistance crystalline reset state and a low-resistance amorphous set state. The inverse resistance change was found to be due to a drastic decrease in the carrier density upon crystallization, which causes a large increase in contact resistivity between CrGT and the electrode. The CrGT memory cell was demonstrated to show fast reversible resistance switching with a much lower operating energy for amorphization than a GeSbTe memory cell. This low operating energy in CrGT should be due to a small programmed amorphous volume, which can be realized by a high-resistance crystalline matrix and a dominant contact resistance. Simultaneously, CrGT can break the trade-off relationship between the crystallization temperature and operating speed.
Displacive transformation is a diffusionless transition through shearing and shuffling of atoms. Diffusionless displacive transition with modifications in physical properties can help manufacture fast semiconducting devices for applications such as data storage and switching. MnTe is known as a polymorphic compound. Here we show that a MnTe semiconductor film exhibits a reversible displacive transformation based on an atomic-plane shuffling mechanism, which results in large electrical and optical contrasts. We found that MnTe polycrystalline films show reversible resistive switching via fast Joule heating and enable nonvolatile memory with lower energy and faster operation compared with conventional phase-change materials showing diffusional amorphous-to-crystalline transition. We also found that the optical reflectance of MnTe films can be reversibly changed by laser heating. The present findings offer new insights into developing low power consumption and fast-operation electronic and photonic phase-change devices.
Cr2Ge2Te6 (CrGT) is a phase change material with higher resistivity in the crystalline phase than in the amorphous phase. CrGT exhibits an ultralow operation energy for amorphization. In this study, the origin of the increased resistance in crystalline CrGT compared to amorphous CrGT and the underlying phase change mechanism were investigated in terms of both local structural change and associated change in electronic state. The density of states at the Fermi level in crystalline CrGT decreased with increasing annealing temperature and became negligible upon annealing at 380 °C. Simultaneously, the Fermi level shifted from the vicinity of the valence band to the band gap center, leading to an increase in resistance. The phase change from amorphous to crystalline CrGT occurred through a metastable crystalline phase with a local structure similar to that of the amorphous phase. Cr nanoclusters were confirmed to exist in both the amorphous and crystalline phases. The presence of Cr nanoclusters induced Cr vacancies in the crystalline phase. These Cr vacancies generated hole carriers, leading to p-type conduction. Photoelectron spectroscopy of the Cr 2s core level clearly indicated a decrease in the fraction of Cr–Cr bonds and an increase in the fraction of Cr–Te bonds in crystalline CrGT upon annealing. Meanwhile, the coordination number of the Cr nanoclusters decreased as the number of Cr–Cr bonds was reduced. Together, these results imply that the origin of the increased resistance in crystalline CrGT is the filling of Cr vacancies by Cr atoms diffusing from Cr nanoclusters.
Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have demonstrated a very strong application potential. In order to realize it, the synthesis of stoichiometric 2D TMDCs on a large scale is crucial. Here, we consider a typical TMDC representative, MoS 2 , and present an approach for the fabrication of well-ordered crystalline films via the crystallization of a thin amorphous layer by annealing at 800 °C, which was investigated in terms of long-range and short-range orders. Strong preferential crystal growth of layered MoS 2 along the ⟨002⟩ crystallographic plane from the as-deposited 3D amorphous phase is discussed together with the mechanism of the crystallization process disclosed by molecular dynamic simulations using the Vienna Ab initio Simulation Package. We believe that the obtained results may be generalized for other 2D materials. The proposed approach demonstrates a simple and efficient way to fabricate thin 2D TMDCs for applications in nanoand optoelectronic devices.
This paper summarizes recent progress on thin film growth of chalcogenides by sputtering. The materials discussed include Sb-Te, Bi-Te, Ge-Te, and their superlattices, materials that are technologically important particularly for non-volatile phase change memory. In this work, the sputter-growth behavior of high-quality layered chalcogenide films is discussed. Sputtering is one of the most commonly used thin-film growth techniques in the semiconductor industry, however, the complex interrelationship between growth parameters can lead to difficulty in fabricating high-quality films although the deposition method itself is relatively simple. Here, we successfully demonstrate the fabrication of highly-oriented layered chalcogenide materials by sputtering. The selection of the appropriate sputtering target is important. In particular, it was found that a Te-rich Sb-Te alloy target such as Sb 33 Te 67 is necessary in order to obtain a stoichiometric Sb 2 Te 3 film. Moreover, the growth temperature is also a key factor in obtaining a highly-oriented film, namely the ideal growth temperature for an Sb 2 Te 3 film is between 230 • C and 250 • C after the growth of an amorphous seed layer at room temperature. Furthermore, it was found that this technique is also useful to grow films epitaxially on Al 2 O 3 or Si(111) substrates even though there are some misoriented grains as well as twins present. Finally, we demonstrate the growth of highly-oriented Sb 2 Te 3 films on a flexible substrate. The versatility of sputtering will become technologically more and more important for the various applications represented by phase change memory.
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.
A Cr 2 Ge 2 Te 6 (CrGT) phase change material (PCM) was studied. Different from conventional PCMs, it shows an inverse resistance change between a low-resistance amorphous phase and a high-resistance crystalline phase. Moreover, the anomalous low resistivity in the amorphous CrGT is considered to be due to a large carrier density, but the mechanism of electrical transport is still not clear. In this study, the electrical transport mechanism of the amorphous CrGT was discussed based on the temperature dependence of the resistivity, carrier density, mobility, and current-voltage characteristics. Above 300 K, the conduction mechanism of the amorphous CrGT was thermally activated band conduction, which is different from the conventional Ge-Sb-Te PCMs that show Poole-Frenkel conduction in the amorphous phase. Below 300 K, the amorphous CrGT shows hopping conduction, changing from variable range hopping (Mott VRH) to Efros-Shklovskii variable range hopping (ES-VRH) with decreasing temperature. The crossover from Mott VRH to ES-VRH was observed at around 200 K. Furthermore, the Fermi level was not pinned at the center of bandgap; instead, it was located near the valence band.
Three-dimensional crossbar technology has been of great significance for realizing high density and multiple terabytes of data storage in memory devices. However, to further scale down the size of memory devices, a selector exhibiting nonlinear electrical properties should be in series with a memory layer in case of unwanted sneak current disturbance. Conventional selectors usually utilize a complicated multilayer structure to realize the high nonlinearity of current, which might be incompatible with certain manufacturing processes or limit the scalability of memory. Herein, we propose a simple heterojunction diode using an n-type oxide semiconductor, specifically, InGaZnO4 (IGZO), and a p-type phase change material (PCM), specifically, N-doped Cr2Ge2Te6 (NCrGT), to realize self-selective performance. The electrode/IGZO/NCrGT/plug-electrode structure with an IGZO/NCrGT pn diode and NCrGT/plug-electrode Schottky diode can realize bidirectional, self-selective phase change random access memory (PCRAM) for either amorphous or crystalline NCrGT. The approximate equilibrium energy band diagrams for the IGZO/NCrGT pn junction and the IGZO/NCrGT/W hybrid junction were proposed to explain the possible conduction mechanism. We demonstrated that hybrid diode-type PCM memory exhibits both selectivity and resistive switching characteristics. The present findings offer new insight into selector technology for PCM.
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