Synthesis and characteristics of Sn-doped SiO2 via plasma-enhanced atomic layer deposition for self-aligned patterning

Sn-doped SiO2 thin films as a spacer for self-aligned patterning were deposited by plasma-enhanced atomic layer deposition and their characteristics were evaluated. This doping research was conducted to improve the mechanical properties of SiO2 films, which have been conventionally used as a spacer material. Because pure SiO2 films have a low Young's modulus, the pattern is stretchable and may collapse as the patterning size decreases. The ratio of the SnO2 and SiO2 deposition cycle was varied from 15(SiO2):1(SnO2) to 3(SiO2):1(SnO2) to modify the film characteristics. X-ray reflectivity (XRR) and time-of-flight secondary ion mass spectrometer analyses revealed whether Sn was doped in SiO2 or became a nanolaminate. The x-ray photoelectron spectroscopy analysis showed that a greater amount of Sn in the SiO2 thin film resulted in a binding energy shift toward the lower binding energy Si2p and Sn3d peaks, and more Si–O–Sn chemical bonding, which increased the number of stiffer ionic bonds as the SnO2 cycle ratio was increased. Therefore, Young's modulus measured by using a nanoindenter increased from 39.9 GPa for SiO2 films to 90.9 GPa for 3(SiO2):1(SnO2) films. However, the hardness results showed a different tendency due to the not well-distributed nanolaminate film structure showing a tendency to decrease and then increase as doping increases. Moreover, the growth rate and film density were evaluated by XRR. The growth per cycle (GPC) of SiO2 was 1.45 Å/cycle and the GPC of SnO2 was 1.0 Å/cycle. The film density of SiO2 was 2.4 g/cm3 and the film density of SnO2 was 4.9 g/cm3. Also, the GPC and film density values of the Sn-doped SiO2 films were in between the values of pure SiO2 and SnO2. The dry etch rate was also measured by reactive ion etching using CF4 plasma with 150 W for 1 min.