Seung Jong Park

Effect of In incorporated into SbTe on phase change characteristics resulting from changes in electronic structure

The effects of the In content of InSbTe films with various stoichiometries (Sb2Te2.7, In0.5Sb2Te2.9, and In2.6Sb2Te2.9) on phase change characteristics were investigated. With increasing incorporation of In atoms into Sb2Te3, various crystalline phases, i.e., In2Te3, Sb, and In3SbTe2, were observed due to the bond energy between the constituent atoms, while only Sb2Te3 and the Sb2Te2 phases were observed in the case of Sb2Te2.7 and In0.5Sb2Te2.9 films. In addition, the shifts in binding energy of the Sb 3d and In 3d peaks in x-ray photoelectron spectra after the annealing treatment were directly related to the amount of incorporated In. The observed changes in electronic structure suggest that the changes in electrical conductivity and crystalline phase are directly related to the extent of In incorporation.

Ultrafast phase change and long durability of BN-incorporated GeSbTe

BN-incorporated amorphous Ge2Sb2Te5 (GST) films were deposited by an ion beam sputtering deposition (IBSD) method using GST and BN targets. Based on in situ sheet resistance measurements, we confirmed that as the amount of BN increased, the crystallization temperature (Tc) increased from 150 °C to 260 °C. It was demonstrated that the phase change speed of BN-incorporated GST is ten times faster than that of GST using a nanosecond laser. By evaluating Johnson–Mehl–Avrami (JMA) plots and scanning electron microscopy (SEM) images, it was confirmed that the one-dimensional grain growth is dominant during the fast phase change of BN-incorporated GST because BN impurities can act like nuclei during the initial stage of crystal growth. After the 100 iteration test under rigorous acceleration conditions of SET/RESET switching using the pulsed laser system, it was confirmed that the void formation and thickness variation are very limited in the BN-incorporated GST, as compared to GST. This result originates from the low phase change stress of the BN-incorporated GST films during one-dimensional growth. The electrical SET speed and cyclability of the BN-incorporated GST device also improved significantly compared to GST.

The Phase Change Effect of Oxygen-Incorporation in GeSbTe Films

Reflectivity changes in oxygen-incorporated Ge 2 Sb 2 Te 5 (GST) films were investigated via a laser-induced crystallization process. The crystallization process showed that the phase change speed and the laser power required for crystallization become faster and larger in GST films with a characteristic quantity of oxygen. We confirmed that a dominant grain growth mode during the laser crystallization is a major determinant for the speed of phase change in GST films with a characteristic quantity of oxygen. JMA results and changes in surface morphology indicate that the origin of the growth mode change is due to an increase in the number of initial nucleation sites produced in the oxygen-incorporated GST films. After the re-amorphization process, oxygen-incorporated GST films show more rapid and more stable phase change properties than that of GST films.

Effect of the Thermal Conductivity on Resistive Switching in GeTe and Ge2Sb2Te5 Nanowires.

The thermal conduction characteristics of GeTe and Ge2Sb2Te5(GST) nanowires were investigated using an optical method to determine the local temperature by Raman spectroscopy. Since the localization of surface charge in a single-crystalline nanostructure can enhance charge-phonon scattering, the thermal conductivity value (κ) of single crystalline GeTe and GST nanowires was decreased significantly to 1.44 Wm(-1) K(-1) for GeTe and 1.13 Wm(-1) K(-1) for GST, compared to reported values for polycrystalline structures. The SET-to-RESET state in single-crystalline GeTe and GST nanowires are characteristic of a memory device. Unlike previous reports using GeTe and GST nanowires, the SET-to-RESET characteristics showed a bipolar switching shape and no unipolar switching. In addition, after multiple cycles of operation, a significant change in morphology and composition was observed without any structural phase transition, indicating that atoms migrate toward the cathode or anode, depending on their electronegativities. This change caused by a field effect indicates that the structural phase transition does not occur in the case of GeTe and GST nanowires with a significantly lowered thermal conductivity and stable crystalline structure. Finally, the formation of voids and hillocks as the result of the electromigration critically degrades device reliability.

Effect of amorphization on the structural stability and reversibility of Ge2Sb2Te5 and oxygen incorporated Ge2Sb2Te5 films

The structural stability of Ge2Sb2Te5 (GST) and oxygen incorporated Ge2Sb2Te5 (GSTO) films was investigated during crystallization and amorphization processes. Variations in the transition temperature for the amorphized films during recrystallization showed that the amorphized GSTO film loses its enhanced amorphous stability due to oxygen incorporation, while the stability is maintained in the GST film. EXAFS and XANES data suggest that a tetrahedral-like Ge–Te(O) bonding structure is generated, forming crystalline and amorphized GSTO films. Moreover, an ab initio XANES simulation indicates that the tetrahedral-like Ge–Te(O) geometry, which is similar to the atomic configuration of the crystalline structure, exists in the form of ordered domains with medium range ordering in the amorphized film. This effect can lead to large variations in Tc and can inhibit reversible phase change characteristics.

Laser irradiation-induced modification of the amorphous phase in GeTe films: the role of intermediate Ge-Te bonding in the crystallization mechanism†

Modified amorphous GeTe, formed by the pulsed laser irradiation of as-grown GeTe, was analyzed in terms of variations in the local bonding structure using Raman spectroscopy and X-ray absorption fine structure in tandem with first-principles density functional theory. Amorphized GeTe (acquired from the crystalline phase) was compared with the modified amorphous GeTe to investigate the similarities and discrepancies between these two amorphous phases. Raman spectroscopy showed that these materials have a similar distribution of Ge-centered local structure in both phases, which is mainly composed of an octahedral-like structure. However, extended X-ray absorption fine structure results show the presence of a unique second type of Ge–Te bonding in the amorphized GeTe, which can effectively reduce the energy required for recrystallization. A computational study based on molecular dynamics simulations verified our experimental observations, including the existence of a second type of Ge–Te bonding in the amorphized phase. Moreover we distinguished the structural characteristics underlying the different amorphous phases, such as local atomic configurations and structural symmetries.

Effects of oxygen incorporation in GeSbTe films on electrical properties and thermal stability

Oxygen incorporated Ge2Sb2Te5 (GST) films were prepared by an ion beam sputtering deposition method. I-V curves of the oxygen incorporated GST active layer showed that the threshold voltage (Vth) varied, depending on the level of incorporated oxygen. In the case of a GST film with an elevated oxygen content of 30.8%, the GST layer melted at 9.02 V due to the instability conferred by the high oxygen content. The formation of Ge-deficient hexagonal phases such as GeSb2Te4 and Sb2Te3 appear to be responsible for the Vth variation. Impedance analyses indicated that the resistance in GST films with oxygen contents of 16.7% and 21.7% had different origins. Thermal desorption spectroscopy data indicate that moisture and hydrocarbons were more readily desorbed at higher oxygen content because the oxygen incorporated GST films are more hydrophilic than undoped GST films.

The origin of the resistance change in GeSbTe films

Amorphous Ge2Sb2Te5 (a-GST) films were deposited by ion beam sputtering deposition. Extended x-ray absorption fine structure (EXAFS) data confirmed the existence of the Ge–Ge homopolar bonds in the films. Raman spectra also indicated that the Ge tetrahedral coordination in the a-GST film disappeared after an annealing treatment above 220 °C. Resonantly excited Ge L2,3 x-ray emission spectra (which probe occupied Ge 3d4s-electronic states) show that the phase change from the amorphous to crystalline state is accompanied by a reduction in the Ge I(L2)/I(L3) intensity ratio due to a L2L3N Coster–Kronig transition, indicating that the number of carriers is increased in the Ge 4sp valence state. These findings constitute direct evidence for the contribution of the Ge electronic states to the resistivity change.

Evolution of crystal structures in GeTe during phase transition

We investigated changes in the crystal structure of GeTe during its phase transition. Using density functional theory (DFT) calculations, four possible crystal structures were identified: R3m, P1, Cm, and Fm3m. Among these, P1 and Cm were examined here for the first time. By calculating the internal energy of the crystal volume change, we verified that P1, R3m, and Cm can coexist in crystalline GeTe. The X-ray diffraction spectra of annealed and laser-irradiated GeTe films revealed coexisting P1 or R3m and Cm. In addition, we confirmed that Cm transforms into P1 or R3m after laser irradiation. The presence of these new structures was revealed in the crystal Raman spectra. Many of the Raman peaks in the crystalized GeTe could be explained by the coexistence of various structures. By calculating the band gaps of these structures, we also found that a structural transformation induces a change in the crystal resistance, owing to differences in the band gaps of individual structures. The generation of new crystal structures suggests a facile phase change and instability during the structural transformation.

Phase-change-induced martensitic deformation and slip system in GeSbTe

Films with a newly observed monoclinic phase of Ge2Sb2Te5 (GST) were analyzed by high-resolution transmission electron microscopy (HRTEM) analysis and ab initio calculations. After an annealing treatment at 220 °C, the amorphous GST films were partly crystallized to an unknown monoclinic crystal structure. The transformation of the face-centered cubic (FCC) phase to monoclinic phases resulted from crystallization-induced stress caused by volume change during FCC formation. The crystallization-induced stress at the amorphous-FCC boundary was estimated to be 1.18 GPa. The volume per atom in the monoclinic phase was about 7.3% greater than that in the FCC phase. The stress value measured in situ was much smaller than the zx stress tensor (shear stress) calculated ab initio because the stress in the actual film was minimized by plastic deformation of the GST itself. Moreover, there is an activation stress barrier to deformation; this barrier corresponds to a deformation angle (γ) of approximately 78°. Slip of the (111) plane along the [110] direction also occurs in the FCC phase during annealing treatment. Based on the calculated total energy difference per atom in GST, the martensitic deformation as well as the slip system can occur at deformation angles as low as 70°.