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.

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.

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.

The electronic structure of the as-deposited amorphous and crystalline phases of transition-metal based Cu2GeTe3 phase-change memory material has been systematically investigated using hard-X-ray photoemission spectroscopy and density-functional theory simulations. We shed light on the role of Cu d electrons and reveal that participation of d electrons in bonding plays an important role during the phase-change process. A large electrical contrast as well as fast switching is preserved even in the tetrahedrally bonded crystal structure, which does not exhibit resonant bonding. On the basis of the obtained results, we propose that transition-metal based phase change memory materials, a class of materials that have been previously overlooked, will be candidates not only for nonvolatile memory applications, but also for emerging applications.

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Cu 2 GeTe 3 (CGT) phase-change material, a promising candidate for advanced fast nonvolatile random-accessmemory devices, has a chalcopyritelike structure with sp 3 bonding in the crystalline phase; thus, the phase-change (PC) mechanism is considered to be essentially different from that of the standard PC materials (e.g., Ge-Sb-Te) with threefold to sixfold p-like bonding. In order to reveal the PC mechanism of CGT, the electronic structure change due to PC has been investigated by laboratory hard x-ray photoelectron spectroscopy and combined first-principles density-functional theory molecular-dynamics simulations. The valence-band spectra, in both crystalline and amorphous phases, are well simulated by the calculations. An inherent tendency of Te 5s lone-pair formation and an enhanced participation of Cu 3d orbitals in the bonding are found to play dominant roles in the PC mechanism. The electrical conductivity of as-deposited films and its change during the PC process is investigated in connection with valence-band spectral changes near the Fermi level. The results are successfully analyzed, based on a model proposed by Davis and Mott for chalcogenide amorphous semiconductors. The results suggest that robustness of the defect-band states against thermal stress is a key to the practical application of this material for memory devices.

The structure of crystal GeCu

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.