Investigation of Fluoro-Carbon Layer on Dense Sicoh Formed during CF4 and CF4/C4F6 Based Continuous Wave Plasma Etch
Authors: Vatsal Abhishek , Oehler Sebastian , Rudolph Matthias , Brackmann Varvara , Bartha Johann W. 
Published: December 2020

Motivation: Plasma etching of low-k and ultra low-k (ULK) dielectric materials have seen a tremendous growth in deep nanoscale applications. Fluorocarbon based gases are the forerunners in etching low-k dielectrics as they are the F suppliers necessary to remove Si and C from SiCOH material. Different FC gases in combination with the additive gases contribute differently to the etch behavior of SiCOH due to differing reaction chemistry and formation of Fluorocarbon layer as an interfacial layer between plasma front and dielectric front [i]. Due to dynamic formation and etching of FC Layer happening at the dielectric surface, understanding FC layer properties in each gas plasma is the starting step to control etch rate and plasma induced damage in Low-k dielectrics. This paper aims to study and compare FC layer deposition by different gases grouped into CF4 and CF4/C4F6 family with N2, O2 and H2 as additive gases in each group. FC layer thickness, etch rate, optical properties of etched SiCOH and chemical composition of the FC layer by different plasma treatments have been presented in this work.

Methodology:

Dense SiCOH (k=2.75 and Open Porosity: 7%) with initial thickness of 157±3nm is deposited on 300mm Si Wafer with a thin SiO2 adhesion layer in between. These wafers are blanket etched in a commercial etch chamber with the given gas combinations (CF4, CF4/N2, CF4/O2, CF4/H2; CF4/C4F6, CF4/C4F6/N2, CF4/C4F6/O2, CF4/C4F6/H2) for same amount of time, total gas flow rate, similar power, pressure and temperature settings.

Post Etch blanket wafers are subjected to various in-line and off-line metrology tools. In-line spectroscopic ellipsometer is used to model complex refractive index and thickness of individual layers. Tauc-Lorentz model best describes the FC layer whereas Cauchy model describes the dielectric [ii]. In-line XPS was carried out to probe the surface of FC layer and gain chemical information. Furthermore depth profile of etched layer is carried out by sputtering the surface with low power Ar ions to study variations in chemical composition with the layer depth. SEM is used to see the cross section profile and verify the results from above method

Observation:

Thickness evaluation from the dispersion models shows that the CF4 group has higher etch rate and lower FC layer thickness compared to CF4/C4F6 group. C4F6 has higher polymerization ability by the virtue of its lower F/C ratio. Amongst each group, Oxygen as additive gas shows the highest etch rate and least FC thickness followed by Nitrogen whereas Hydrogen has least etch rate but highest FC layer thickness. Under given etch conditions with CF4/C4F6/H2 plasma, deposition rate was higher than etching rate leading to stack growth (Fig.1a). Hydrogen supports polymerization by scavenging Fluorine away and aids in thicker FC films.

XPS chemical composition shows Fluorine diffusion through FC layer into the dielectric layer bringing changes to its pristine structure. This affects Carbon% across the etched dielectric thickness (Fig.1b). Thicker the FC layer is, closer is the Carbon % to pristine SiCOH. Presence of surficial Nitrogen in the nitrogen containing plasmas shows nitrogen reacts with SiCOH Carbon, forms CN compounds and increases the etch rate. FC layer shows presence of CF3 radicals on the surface and decrease fast with the depth, followed by CF2 radicals. CF radicals are in larger quantity and are present deepest into the FC Layer. Presence of polymerized C-C and C-CFx bonds increases with the FC Layer depth and offset with increase of C-Si bond near the SiCOH interface.

Conclusion: This paper shows comparison of Etch Rate and FC layer thickness during SiCOH etch using different gas combinations in the CCP plasma chamber. Thickness correlation between ellipsometric model data and XPS depth profile followed by SEM cross section measurement of layer thickness point towards the correctness of dispersion models for each layer. These models can be used for quick inline post etch metrology useful for process control. O2 containing plasmas are too aggressive on the dielectric with negligible FC layer formation, while H2 containing plasmas are less damaging but exhibit very small etch rate. CF4/C4F6/N2 plasma is the optimum combination for Low-k dielectric etch amongst other combinations in terms of desired etch rate and lower reduction in Carbon %. Relative concentration and penetration depth of different CFx radicals in FC film suggests its influence on film structure.

References:

Baklanov et.al, Journal of Applied Physics 113, 041101 (2013); doi: 10.1063/1.4765297

T. Easwarakhanthan et al., Journal of Applied Physics 101, 073102 (2007); doi: 10.1063/1.2719271

Figure 1