Kazuyuki Tomida

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

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...

Considerations for further scaling of metal–insulator–metal DRAM capacitors

Effective electron tunneling mass mtunnel is extracted from trap-assisted leakage in Sr-rich strontium titanate and rutile titanium oxide films in metal–insulator–metal (MIM) capacitors and compared with theoretical values obtained from first principles calculations of the imaginary band structure. Optimum orientations of films and stoichiometry impacting mtunnel are also discussed. Because future vertical DRAM integration schemes also stipulate maximum thickness of the MIM capacitor, mtunnel is shown to be a critical parameter influencing intrinsic leakage and potentially limiting further scaling.

Impact of thermal treatment upon morphology and crystallinity of strontium titanate films deposited by atomic layer deposition

Strontium titanate (STO) is a dielectric with a cubic perovskite type structure and of increasing interest for microelectronics, especially in the metal-insulator-metal (MIM) capacitors due to its high dielectric constant. The dielectric constant of the STO films and consequently the performance of the MIM capacitors appear to be strongly influenced by the process conditions. In this work the authors report on the influence of various thermal treatments upon the crystallinity and morphology of strontium titanate crystals. The influence of spike, laser, or rapid thermal anneals on the morphology with respect to grain size and topography of the crystalline stoichiometric STO films is studied. Also, the use of a stack containing a Sr-rich STO (62% Sr) bottom seed layer and a stoichiometric STO top layer in combination with a thermal treatment was found to affect the microstructure of the STO film. A comparison of the electrical properties for various thermal treatments has been made.

High-k Dielectrics and Metal Gates for Future Generation Memory Devices

The requirements and development of high-k dielectric films for application in storage cells of future generation flash and Dynamic Random Access Memory (DRAM) devices are reviewed. Dielectrics with k-value in the 9-30 range are studied as insulators between charge storage layers and control gates in flash devices. For this application, large band gaps (> 6 eV) and band offsets are required, as well as low trap densities. Materials studied include aluminates and scandates. For DRAM metal-insulator-metal (MIM) capacitors, aggressive scaling of the equivalent oxide thickness (with targets down to 0.3 nm) drives the research towards dielectrics with k-values > 50. Due to the high aspect ratio of MIMCap structures, highly conformal deposition techniques are needed, triggering a substantial effort to develop Atomic Layer Deposition (ALD) processes for the deposition of metal gates and high-k dielectrics. Materials studied include Sr and Ba-based perovskites, with SrTiO3 as one of the most promising candidates, as well as tantalates, titanates and niobates.

Growth and Material Characterization of Hafnium Titanates Deposited by Atomic Layer Deposition

Hafnium titanate (HTO) films were deposited within a large Hf-Ti compositional range by atomic layer deposition using HfCl4/TiCl4/H2O precursors. The Hf content of the layers is well controlled by the precursor pulse ratio, as indicated by Rutherford backscattering. The saturation conditions of ternary HTOs are different compared to those of the binary oxides, First-principles simulation confirmed the enhancement of the Hf precursor reactivity in the presence of Ti-OH. Growth curves of HTOs showed a good linearity with the number of reaction cycles. A linear correlation between density, quantified by X-ray reflectometry, and composition was observed. X-ray diffraction indicated that the as-deposited films are amorphous up to 500-700 degrees C, depending on the Hf/Ti ratio. The orthorhombic HfTiO4 diffraction lines in the samples (30-64% Hf) annealed at 850 degrees C were observed. For a Hf content higher than 82%, a monoclinic HfO2-Iike structure was reported. The dielectric constant and leakage current depend on the Ti content, the film crystallinity, and the anneal atmosphere. The posideposition anneal in O-2, is found to have a drastic effect in leakage Current density reduction and could be a key for further improvements of HTO electrical properties.

Non-linear dielectric constant increase with Ti composition in high-k ALD-HfTiOx films after O2 crystallization annealing

HfTiOx films deposited on TiN, Pt and Al2O3/Si bottom electrodes (BE) by Atomic Layer Deposition (ALD) method were investigated in terms of the crystallization temperature, dielectric constant and leakage current. The as-deposited films show a linear increase of dielectric constant from 20 (HfO2) to 40 (TiO2) as a function of Ti content in the film. On the other hands, the dielectric constant of HfTiOx films with 64% – 30% Hf content increases up to 60 after crystallization annealing, which strongly correlates with the appearance of the orthorhombic HfTiO4 structure. Furthermore, the thermal treatment in O2 ambient is found to have a drastic effect to decrease the leakage current density (Jg). As a result, 10−8 A/cm2 at Vg = +1V with 0.8nm EOT is achieved with 30%-Hf contained film.

Understanding of Trap-Assisted Tunneling Current - Assisted by Oxygen Vacancies in RuOx/SrTiO3/TiN MIM Capacitor for the DRAM Application

A transient leakage current was measured as a function of time for thin (~9 nm) strontium titanate (STO) capacitor dielectrics with RuOx as a bottom electrode and TiN as a top electrode at different temperatures under constant direct current (DC) bias stress. With the space-charge-limited (SCL) current theory, the mobility of oxygen vacancies (VO) and the activation energy (E0) of VO were extracted. By closely examining the time-zero current-voltage (I-V) curves for a positively and a negatively held DC bias conditions before and after the stresses, an understanding of trap-assisted-tunneling (TAT) current, initiated by oxygen vacancies (VO) is presented. Based on this understanding, a way to further reduce the leakage current for a sub-10 nm dielectric film is provided.