Emerging devices (Logic and Advanced Memory) require high quality thin (5-20 Å) electrode and barrier films. Difficult thermal budget constraints are now being placed on well-known materials such as TiN and TaN. Deposition temperature limitations have reached 350°C and below while very low resistivity (<100 micro-ohm/cm) must be achieved. Novel Ti precursors are being explored.1 Our approach has focused on hydrazine (N2H4) as an alternative nitrogen source to NH3. Hydrazine is generally difficult to handle from a safety perspective due to its flammability and toxicity. We have developed a novel method to store and generate hydrazine in situ as a high purity gas which is then delivered to ALD process chambers.2 In this study, we examine the effect that hydrazine has on low deposition temperature TiN ALD processes. We experimentally evaluate TiN ALD growth and film characteristics using TiCl4/ N2H4 in comparison to that using TiCl4/NH3. Titanium Nitride films were deposited using the hot wall type tubular furnace and a sequential gas supply system. Deposition temperature was set to predetermined value in the range from 250°C to 400°C. In the case of TiCl4/NH3, GPC was 0.10-0.27 Å/cycle at 250-400°C, where a decrease is noted as the deposition temperature is reduced. With the use of hydrazine, an increase in GPC is observed at each deposition temperature vs NH3. Moreover, the temperature dependence of GPC moved in the opposite direction of TiCl4/NH3. Specifically, GPC of TiCl4/N2H4 ALD was 19% higher at 400°C while an increase of 310% was seen at 250°C versus NH3. In the case of TiCl4/N2H4, the ALD window appears in the range of 250-400°C, where TiCl4 adsorption saturation curves are observed at 250°C and 400°C. Refractive index (R.I.) of TiCl4/N2H4 ALD was about 1.68-1.73 at 250-400°C. These values were approximately equal to R.I. of typical sputtered TiN which was about 1.66. In contrast, R.I. of TiCl4/NH3 ALD was larger than 2.00 in the 250- 300°C range. Because of R.I. of typical titanium oxide is about 2.4-2.5, it is assumed that the TiCl4/NH3 ALD film is contaminated by oxygen. In the ammonia case, background contaminants in the reactor appear to compete with low reactivity NH3 for reaction sites on the ALD surface. In the TiCl4/N2H4 case, higher temperature is not required to form high quality TiN films compared to TiCl4/NH3 ALD. From the above results, the use of high purity hydrazine is beneficial to maintaining high throughput and good film quality under the new constraints for emerging devices. Film composition by XPS and Resistivity measurements consistent with this conclusion will also be presented. References [1] Klesko J.P., Thrush C.M., Winter C.H., Chemistry of Materials. 27: 4918-4921, (2015). [2] J. Spiegelman, Daniel Alvarez et al., 18th International Conference on Atomic Layer Deposition (2018) AMTuP2. Figure 1
Increased Hydrophilicity of Silicon Surface through Plasma Treatment with Hydrogen Peroxide Gas Spiegelman, D. Alvarez, C. Ramos (RASIRC), K. Andachi, G. Tsuchibuchi, and K. Suzuki (Taiyo Nippon Sanso Corporation) Wafer bonding is a critical step in the development of advanced semiconductor and MEMS devices.1 Wafer bonding enables the bonding of dissimilar materials as well as the union of separate manufacturing pathways where the pathway steps are dissimilar and frequently incompatible to a single wafer process. Oxide wafer bonding is a common bonding method that requires the wafer surface to have a uniformly flat surface with sufficiently dense hydroxyl (-OH) groups. The hydroxyl groups provide a pathway for chemical covalent bonding between two wafer surfaces (EG Si-O-Si). Ultimately, the wafer bonding strength is a function of the density of the hydroxyl groups populated on the wafer surface before bonding. Several challenges are associated with functionalizing wafer surfaces. Wet Thermal oxidation is a common method for incorporating surface hydroxyl groups on silicon, however this process typically takes place at very high temperatures (>600C °) where surface hydroxyl groups may reversibly desorb, thus limiting surface functionalization. Surface oxidation by Oxygen plasma is another common method for the creation of hydrophilic surfaces,2 however, this property may be attributed to bridging oxides on the surface, where hydroxyl groups may not be present. In the latter case, residual charge or surface radical species may lead to the observed improvement in wafer bonding properties. Plasma oxidation allows for lower temperature activation.2 Oxygen or clean dry air are frequently used in the plasma process with argon. Our investigation involves the use of hydrogen peroxide gas. In recent years this material has become available in the gas phase where: Gas-phase H2O2/H2O mixture is delivered from an ampoule-based formulation. (RASIRC® BRUTE® Peroxide) High concentration H2O2/H2O is vaporized by in situ concentration methods and use of a membrane vaporizer as a gas generator. (RASIRC Peroxidizer®) Early studies by Kummel3 demonstrated that Hydrogen peroxide gas provides a denser hydroxyl surface on SiGe and Ge vs water. Here, all thermal methods were utilized at reduced temperatures. Before our current work, the creation and use of gas-phase hydrogen peroxide plasma has not been addressed. The objective of this work is to demonstrate the generation of hydrogen peroxide plasma and compare its surface functionalization characteristics to those of water and oxygen plasma methods. A constant gas stream of H2O2/H2O mixture in a carrier gas was introduced to a remote plasma source (MKS). (Figure 1). The use of an argon carrier gas led to stable ignition of the plasma mixture. The subsequent addition of oxygen gas gives rise to plasma instability. In the comparative study, the H2O2 gas stream was mixed with water vapor, molecular oxygen, and argon in different ratios, subjected to a remoted plasma. Functionalization was then carried out on a Si-H terminated surface (HF last silicon wafer surface). Thermal effects without plasma were also compared. Surface hydrophilicity (relative Hydroxyl density) was determined by contact angle measurements with the use of a goniometer. The initial wafer surface after HF clean had a water contact angle of 84.9 °. The smallest wetting angle was found for H2O2/H2O/Ar plasma at 4 °. Water alone led to a wetting angle that was 62.5% larger than the hydrogen peroxide mixture. The angle increased with increasing oxygen concentration in the H2O2 gas stream. The wetting angle with dry oxygen at 200C ° was 27.3°. Thermal only H2O2 gas at 150C° was 47.3 ° and further reduced to 11.4 ° when the temperature was increased to 300C °. (Figure 2). These results along with mechanism and ramifications for wafer bonding will be discussed. References: Rogers, T.; Aitken, N.; ECS Trans. 16, 507, (2008). Howlader, M.M.R, Suga, T.; J. Micro/Nanolith. MEMS MOEMS 9(4), 1-11 (2010). Park, S.W. et al. Surface Science 652 322–333, (2016).
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.