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The discovery of ferroelectricity in HfO2-based materials in 2011 provided new research directions and opportunities. In particular, for atomic layer deposited Hf0.5Zr0.5O2 (HZO) films, it is possible to obtain homogenous thin films with satisfactory ferroelectric properties at a low thermal budget process. Based on experiment demonstrations over the past 10 years, it is well known that HZO films show excellent ferroelectricity when sandwiched between TiN top and bottom electrodes. This work reports a comprehensive study on the effect of TiN top and bottom electrodes on the ferroelectric properties of HZO thin films (10 nm). Investigations showed that during HZO crystallization, the TiN bottom electrode promoted ferroelectric phase formation (by oxygen scavenging) and the TiN top electrode inhibited non-ferroelectric phase formation (by stress-induced crystallization). In addition, it was confirmed that the TiN top and bottom electrodes acted as a barrier layer to hydrogen diffusion into the HZO thin film during annealing in a hydrogen-containing atmosphere. These features make the TiN electrodes a useful strategy for improving and preserving the ferroelectric properties of HZO thin films for next-generation memory applications.

High density plasma etching of Pd thin films masked with TiN films was performed using CH3OH/Ar, C2H5OH/Ar, CH4/Ar, and CH4/O2/Ar gas mixtures. The etch rates of the Pd films and TiN masks in all the gas mixtures decreased whereas the etch selectivities increased. The etch profiles of the Pd films etched under C2H5OH/Ar gas were better than those obtained with CH3OH/Ar gas. Addition of O2 gas to the CH4/Ar gas mixture considerably improved the etch profiles of the Pd films. CH4, Ar, and O2 were found to play a critical role in obtaining a vertical etch profile with smooth sidewalls. Energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy revealed the formation of polymeric layers and PdOx compounds on the sidewalls and the film surface. Good etch profiles with a high degree of anisotropy were achieved with the use of C2H5OH/Ar and CH4/O2/Ar gas mixtures.

Inductively coupled plasma reactive ion etching of Ta thin films masked with photoresist was performed using C2F6/Ar, HBr/Ar and Cl2/Ar gases. The etch characteristics such as etch rate, etch selectivity and etch profile were investigated in different gas concentrations of each gas. The Cl2 chemistry showed high degree of anisotropy in etch profile as well as fastest etch rate and highest etch selectivity of Ta films among these gases. Optical emission spectroscopy revealed that the increase in chlorine radicals with increasing Cl2 concentration was responsible for the increase in the Ta etch rate. The etch rate of Ta films increased with increasing ICP rf power and dc-bias voltage, and decreasing process pressure. Good etch profiles were obtained at high rf power and dc-bias voltage, and low process pressure. X-ray photoelectron spectroscopy confirmed the existence of a chemical reaction of Ta with chlorine radicals by forming tantalum chlorides. These results suggested that Ta etching in Cl2/Ar follows the typical reactive ion etching mechanism. It was concluded that a high degree of anisotropy and high etch rate of Ta films were achieved using Cl2/Ar gas.

The etch characteristics of Ru thin films patterned with TiN hard masks in O 2 /Ar, CH 4 /Ar and O 2 /CH 4 /Ar gas mixtures were studied using inductively coupled plasma reactive ion etching. When the Ru films were etched in O 2 /Ar gas, the etch rates of the Ru films and TiN hard masks decreased but the etch selectivity of the Ru films to the hard mask increased with increasing O 2 concentration. The etch profiles of Ru films at various O 2 concentrations were very similar, showing high etch slopes of > 80° with uneven sidewalls. In the case of CH 4 /Ar gas, as the CH 4 concentration increased, the etch rates of the Ru films and TiN hard masks and the etch selectivity of Ru films decreased. The etch profile of Ru films etched in 20% CH 4 /Ar showed the etch slope of approximately 60° and the etch slopes became worse with increasing CH 4 concentration. The addition of O 2 to the CH 4 /Ar gas resulted in a significant improvement in the etch profile, but both etch rates decreased slightly. Optical emission spectroscopy of O 2 /CH 4 /Ar plasma showed that O species could oxidize the Ru films to RuO x , and that inhibition layers containing C or CH x were formed, which protected the pattern sidewalls. X-ray photoelectron spectroscopy also identified the formation of RuO x and C or CH x compounds on the film surface. These findings indicated that Ru etching in O 2 /CH 4 /Ar gas chemistry could provide a good etch profile without redeposition or etch residues.

Copper is widely used in the semiconductor industry as interconnects due to its low resistivity, high resistance to electromigration, low temperature coefficient of resistance, and good thermal stability (1). As advanced nanoelectronics has moved towards the sub-5 nm node technology and beyond, the back-end of line interconnects process is scaled down to smaller pitch sizes with a lot of challenges (2,3). Recently, area-selective atomic layer deposition (AS-ALD) by locally passivating the surface has garnered attention as it can lead to a paradigm shift from today’s top-down VLSI fabrication by not only reducing the number of processing steps but also by alleviating key challenges associated with lithography and layer alignment at the sub-5 nm node (4). However, there are still several challenging factors to implement them in the process node successfully. Despite the enormous scientific effort in recent years, lack of surface science during cleaning and passivation of Cu surfaces impede the development of AS-ALD. Specifically, the initial surface condition of Cu films can affect not only a cleaning surface (i.e., adventitious contaminants and CuxO) but also further passivation process using a self-assembled monolayer (SAMs). Recently, the reduction of the Cu surface using vapor-phase N2H4 has been reported due to its higher reduction capability (4,5). Herein, the effect of the initial surface condition of Cu samples on both cleaning and passivation of the surfaces was investigated. Electroplated Cu films were pretreated using anhydrous N2H4 for vapor phase surface cleaning. Reflectance absorption infrared spectroscopy (RAIRS) with ALD capability was employed to elucidate the surface chemistry. During surface cleaning, N2H4 reduces the surface oxide (Cu2O) to metallic copper as well as remove adventitious surface contaminants (e.g., –CHx, –CO3, and –OH). In the case of cleaning with CH3COOH, the Cu surface reduces the surface oxide (Cu2O) to metallic copper, importantly the copper acetate which might be the intermediate material was formed after cleaning. After pretreatment, each Cu sample was immersed into 1 mM octadecanethiols (ODTs) in ethanol for 20 hours, then ALD of AlOx using TMA and H2O was performed at 120 oC. The N2H4-treated Cu sample shows better physical and chemical stability during ALD process, resulting in good selectivity compared to the SAMs on the as-is Cu. The detailed experimental results will be presented. This work is supported by Rasirc Inc. by providing the anhydrous N2H4. This work was also partly supported by the Fostering Global Talents for Innovative Growth Program (No. P0008750) through KIAT and MOTIE. J. Ahn and J. Kim also acknowledge partial financial supports by Brain Pool Program through National Research Foundation by the Ministry of Science and ICT in Korea (Grant #: 2019H1D3A2A01101691). R. P. Chaukulkar, N. F. W. Thissen, V. R. Rai, and S. Agarwal, J. Vac. Sci. Technol. A, 32, 01A108 (2014). L. F. Pena, J. F. Veyan, M. A. Todd, A. Derecskei-Kovacs, and Y. J. Chabal, ACS Appl. Mater. Interfaces, 10, 38610–38620 (2018). M. He et al., J. Electrochem. Soc., 160, D3040–D3044 (2013). D. M. Littrell, D. H. Bowers, and B. J. Tatarchuk, J. Chem. Soc. Faraday Trans. 1 Phys. Chem. Condens. Phases, 83, 3271–3282 (1987). S. M. Hwang et al., ECS Trans., 92, 265–271 (2019). Figure 1

The etch characteristics of TiN hard mask patterned CoFeB thin films were investigated using an inductively coupled plasma reactive ion etching in a CH3COOH/Ar gas mixture. The etch characteristics of CoFeB magnetic thin film and TiN hard masks were investigated as a function of gas mixture concentration, coil rf power, dc-bias voltage and gas pressure. As CH3COOH concentration in the CH3COOH/Ar gas mixture increased, the etch rates of CoFeB films and degree of anisotropy in the etch profile decreased, while increased coil rf-power and dc bias voltage and reduced gas pressure increased the etch rate and improved the etch profile. Additionally, a thick hydrocarbon layer was formed on the film surface at a dc-bias voltage of 100 V. X-ray photoelectron spectroscopy and optical emission spectroscopy analyses of the etched films at various CH3COOH concentrations suggest that CoFeB thin films etched in a CH3COOH/Ar gas mixture follow a physical sputtering etch mechanism assisted by oxidation of the film and formation of a protective inhibition layer on the film surface. Etching of TiN patterned CoFeB films with a high degree of anisotropy was accomplished without redepositions or etch residues when conducted under high sputtering conditions.

Inductively coupled plasma reactive ion etching (ICPRIE) of Ru thin films patterned with TiN hard masks was investigated using a CH3OH/Ar gas mixture. As the CH3OH concentration in CH3OH/Ar increased, the etch rates of Ru thin films and TiN hard masks decreased. However, the etch selectivity of Ru films on TiN hard masks increased and the etch slope of Ru film improved at 25% CH3OH/Ar. With increasing ICP radiofrequency power and direct current bias voltage and decreasing process pressure, the etch rates of Ru films increased, and the etch profiles were enhanced without redeposition on the sidewall. Optical emission spectroscopy and X-ray photoelectron spectroscopy were employed to analyze the plasma and surface chemistry. Based on these results, Ru thin films were oxidized to RuO2 and RuO3 compounds that were removed by sputtering of ions and the etching of Ru thin films followed a physical sputtering with the assistance of chemical reaction.

The inductively coupled plasma etching characteristics of Co2MnSi thin films patterned using a TiN hard mask were investigated by the addition of CH3OH to Ar gas. As the CH3OH concentration increased, the etch rates of Co2MnSi magnetic thin films and TiN hard mask decreased, but the etch profile improved. The effects of rf power, dc-bias voltage and gas pressure on the etch rate and etch profile were also investigated. The etch rate and etch profile degree of anisotropy increased with increasing rf power and dc-bias voltage and decreasing gas pressure. Optical emission spectroscopy analysis revealed that [H], [O], [CO], [OH], [CH3O] and [Ar] species in the CH3OH/Ar plasma played a key role in achieving a good etch profile.

High density plasma etching of MgO thin films patterned with Ti (or TiN) hard masks was conducted using Cl2/Ar, CH3OH/Ar and CH4/Ar gases. As the concentration of each gas increased, the etch rate of MgO thin films decreased and there was no enhancement of etch profiles except for those obtained using CH4/Ar gas. The etch profiles of MgO thin films under CH4/Ar gas, which is non-corrosive and non-toxic, were improved without redeposition with increasing CH4 concentration. The enhancement of etch profiles in CH4/Ar gas was attributed to both the formation of a protective layer containing hydrogen and hydroxyl species on the sidewall of the patterns and the formation of magnesium compounds during the etching. Optical emission spectroscopy and X-ray photoelectron spectroscopy analyses showed that magnesium hydroxide was formed due to chemical reactions on the film surface under CH4/Ar gas. Additionally, the MgO thin films were found to be etched by a physical sputtering etching mechanism that was influenced by a chemical reaction.

The ferroelectric (FE) properties of 10-nm-thick Hf0.5Zr0.5O2 (HZO) films deposited by an atomic layer deposition technique were improved by adopting O3 as an oxygen source instead of H2O. All HZO films were annealed at 400 °C for 1 min in an N2 atmosphere after TiN top electrode deposition. Regardless of the oxygen source, the HZO films exhibited the formation of a noncentrosymmetric orthorhombic phase, which is responsible for FE behavior with the suppression of the monoclinic phase. However, compared to the O3-based HZO film, it was confirmed that the H2O-based HZO film was more incorporated with hydrogen derived from H2O, thereby degrading FE polarization and leakage behavior. The results indicate that the strategy of using O3 as the oxygen source is useful for the fabrication and integration of FE HZO films for next-generation memory applications.

Zn(O,S) thin films were successfully deposited by reactive sputtering using Ar and O2 gas mixtures at 473 K. X-ray diffraction patterns revealed that the well crystallized Zn(O,S) films were deposited with increasing oxygen concentration in O2/Ar, resulting in a shift of the Zn peak of 28.5° to a higher angle, closer to the ZnO peak of 34.4°. Zn(O,S) films were composed of grains agglomerated from small particles, which grew gradually with increasing oxygen concentration. The depth profiles and energy dispersive spectroscopy results of the films indicated that the O/(O+S) ratio increased from 0.04 to 0.81, and all Zn(O,S) films were Zn rich with uniform concentrations of each component. X-ray photoelectron spectroscopy revealed that, as the oxygen concentration increased to 2%, the ZnS films were transformed to Zn(O,S) films via substitution of oxygen for sulfur.

Co2MnSi thin films masked with TiN films were etched in CH4/Ar and CH4/O2/Ar plasmas by inductively coupled plasma reactive ion etching. The etch rates decreased with increasing CH4 concentration in CH4/Ar gas, whereas the etch selectivity increased. The addition of O2 to CH4/Ar gas resulted in significant improvement in the etch profile but a decrease in the etch rates. Optical emission spectroscopy showed that a variety of COx, OH, and H2O species were formed in the CH4/O2/Ar plasma, acting a role as a passivation layer to protect the pattern sidewalls. X-ray photoelectron spectroscopy also confirmed the formation of metal oxides on the film surface, which could be sputtered off easily by Ar ion bombardment. A high degree of anisotropy of Co2MnSi films was obtained in the CH4/O2/Ar etch gas.