Sergiu Clima

10×10nm 2 Hf/HfO x crossbar resistive RAM with excellent performance, reliability and low-energy operation

We report on worlds smallest HfO2-based Resistive RAM (RRAM) cell to date, featuring a novel Hf/HfOx resistive element stack, with an area of less than 10×10 nm2, fast ns-range on/off switching times at low-voltages and with a switching energy per bit of <0.1pJ. With excellent endurance of more than 5.107cycles, large on/off verified-window (>50), no closure of the on/off window after 30hrs/200C and failure-free device operation after 30hrs/250C thermal stress, the major device-level nonvolatile memory requirements are met. Furthermore, we clarify the impact of film crystallinity on cell operation from a scalability viewpoint, the role of the cap layer and bring insight into the switching mechanisms.

Endurance/Retention Trade-off on

The endurance/retention performance of HfO2/ Metal cap RRAM devices in a 1T1R configuration shows metal cap dependence. For Hf and Ti caps, owning strong thermodynamic ability of extracting oxygen from HfO2, long pulse endurance (>1010 cycles) could be achieved. For Ta cap, owning lower thermodynamic ability of extracting oxygen from HfO2, better retention can be achieved. Therefore, an endurance/retention performance tradeoff is identified on the 40 nm × 40 nm HfO2/Metal cap bipolar RRAM devices. The tradeoff of endurance/retention performance can be explained by a different filament constriction shape depending on metal cap layer as derived from fitting I-V curves in the quantum point contact model. This difference in filament constriction shape is attributed to the thermodynamics difference of metal cap: Hf and Ti have a stronger thermodynamical ability to extract oxygen from HfO2 than Ta. The possibility of tuning the intrinsic reliability performance by changing the cap materials paves a way for optimizing the operation of RRAM devices into the desired specifics.

\hbox{HfO}_{2}/\hbox{Metal}

An analytic dynamic hour glass model for HfO2 RRAM is demonstrated, describing the reset as a dynamic equilibrium process and the set as a constriction growth limited by ion mobility and current compliance. The dependence on time, voltage and forming conditions is in good constriction growth agreement with experiments. Since the model is fully analytical, it can be implemented in a circuit simulator.

Cap 1T1R Bipolar RRAM

One of the key concerns related to low operating current (<;50μA) of RRAM is the degraded data retention. Most of the retention studies so far focused on high switching current range. In this work, we investigate the retention degradation mechanism at low programming current range (10-40μA) and identify the key parameters that control retention in oxygen vacancy filamentary switching HfO<;sub>2<;/sub>/Hf 1T1R RRAM cells. Based on this understanding we demonstrated significant improvement in retention by adding an additional thermal budget into our process flow. The impact of the Forming process on retention property was also investigated and Forming/SET conditions were optimized to improve the retention without increasing the operation current.

Dynamic ‘hour glass’ model for SET and RESET in HfO 2 RRAM

Transition metal oxide-based resistor random access memory (RRAM) takes advantage of oxygen-related defects in its principle of operation. Since the change in resistivity of the material is controlled by the oxygen deficiency level, it is of major importance to quantify the kinetics of the oxygen diffusion, key factor for oxide stoichiometry. Ab initio accelerated molecular dynamics techniques are employed to investigate the oxygen diffusivity in amorphous hafnia (HfOx, x = 1.97, 1.0, 0.5). The computed kinetics is in agreement with experimental measurements.

Improvement of data retention in HfO 2 /Hf 1T1R RRAM cell under low operating current

In this work, the physical and electrical properties of SrxTi1−xOy (STO)-based metal-insulator-metal capacitors (MIMcaps) with various compositions are studied in detail. While most recent studies on STO were done on noblelike metal electrodes (Ru, Pt), this work focuses on a low temperature (250 °C) atomic layer deposition (ALD) process, using an alternative precursor set and carefully optimized processing conditions, enabling the use of low-cost, manufacturable-friendly TiN electrodes. Physical analyses show that the film crystallization temperature, its texture and morphology strongly depends on the Sr/Ti ratio. Such physical variations have a direct impact on the electric properties of SrxTi1−xOy based capacitors. It is found that Sr-enrichment result in a monotonous decrease in the dielectric constant and leakage current as predicted by ab initio calculations. The intercept of the EOT vs physical thickness plot further indicates that increasing the Sr-content at the film interface with the bottom TiN...

First-principles simulation of oxygen diffusion in HfOx: Role in the resistive switching mechanism

The origin of the ferroelectric polarization switching in orthorhombic HfO2 has been investigated by first principles calculations. The phenomenon can be regarded as being the coordinated displacement of four O ions in the orthorhombic unit cell, which can lead to a saturated polarization as high as 53 μC/cm2. We show the correlation between the computed polarization reversal barrier and the experimental coercive fields.

Composition influence on the physical and electrical properties of SrxTi1−xOy-based metal-insulator-metal capacitors prepared by atomic layer deposition using TiN bottom electrodes

Bipolar switching transition metal-oxide (TMO) RRAM devices are intensively studied as possible non-volatile memory for 1x nm node. HfO2 based stacks with excellent operation, good endurance and retention have been proposed [1, 2, 3], with demonstrated scalability down to <;10nm [3]. However, characterization of the reliability failure modes and understanding of the degradation mechanism is urgently needed, especially in the low operation current range relevant for practical application of RRAM devices. Although retention and endurance models in different TMO have been proposed [4, 5, 6], an in-depth understanding of endurance is still lacking for scaled HfO2 RRAM in low current operation.

Identification of the ferroelectric switching process and dopant-dependent switching properties in orthorhombic HfO2: A first principles insight

In this article, we present a fragment model potential approach for the description of the crystalline environment as an extension of the use of embedding ab initio model potentials (AIMPs). The biggest limitation of the embedding AIMP method is the spherical nature of its model potentials. This poses problems as soon as the method is applied to crystals containing strongly covalently bonded structures with highly nonspherical electron densities. The newly proposed method addresses this problem by keeping the full electron density as its model potential, thus allowing one to group sets of covalently bonded atoms into fragments. The implementation in the MOLCAS 7.0 quantum chemistry package of the new method, which we call the embedding fragment ab inito model potential method (embedding FAIMP), is reported here, together with results of CASSCF/CASPT2 calculations. The developed methodology is applied for two test problems: (i) the investigation of the lowest ligand field states (2)A1 and (2)B1 of the Cr(V) defect in the YVO4 crystal and (ii) the investigation of the lowest ligand field and ligand-metal charge transfer (LMCT) states at the Mn(II) substitutional impurity doped into CaCO3. Comparison with similar calculations involving AIMPs for all environmental atoms, including those from covalently bounded units, shows that the FAIMP treatment of the YVO4 units surrounding the CrO4(3-) cluster increases the excitation energy (2)B1 → (2)A1 by ca. 1000 cm(-1) at the CASSCF level of calculation. In the case of the Mn(CO3)6(10-) cluster, the FAIMP treatment of the CO3(2-) units of the environment give smaller corrections, of ca. 100 cm(-1), for the ligand-field excitation energies, which is explained by the larger ligands of this cluster. However, the correction for the energy of the lowest LMCT transition is found to be ca. 600 cm(-1) for the CASSCF and ca. 1300 cm(-1) for the CASPT2 calculation.

Understanding of the endurance failure in scaled HfO 2 -based 1T1R RRAM through vacancy mobility degradation

We report a novel self-compliant and self-rectifying resistive switching memory cell, with area-scalable switching currents, featuring a set current density of ~5nA/nm2 (<;9uA for a 40nm-size cell), high on-state half-bias nonlinearity of 102 and low reset current density of <;0.6nA/nm2 (<;1uA@40nm size). The cell can be operated at below ±4V/10ns, with a large on/off window of >102 and retention extrapolates to 10yr at 101°C. The switching stack is fully based on ALD processes, using common high-k dielectrics and has a thickness of <;10nm, meeting the 3D Vertical RRAM requirements. Moreover, we point out the nonlinearity-low-current operation interdependence and discuss the scaling potential of the areal switching RRAM for reliable sub-μA current operation in the 10nm-cell size realm.