No abstract

Silicon nitride (SiNx) thin films using 1,3-di-isopropylamino-2,4-dimethylcyclosilazane (CSN-2) and N2 plasma were investigated. The growth rate of SiNx thin films was saturated in the range of 200–500 °C, yielding approximately 0.38 Å/cycle, and featuring a wide process window. The physical and chemical properties of the SiNx films were investigated as a function of deposition temperature. As temperature was increased, transmission electron microscopy (TEM) analysis confirmed that a conformal thin film was obtained. Also, we developed a three-step process in which the H2 plasma step was introduced before the N2 plasma step. In order to investigate the effect of H2 plasma, we evaluated the growth rate, step coverage, and wet etch rate according to H2 plasma exposure time (10–30 s). As a result, the side step coverage increased from 82% to 105% and the bottom step coverages increased from 90% to 110% in the narrow pattern. By increasing the H2 plasma to 30 s, the wet etch rate was 32 Å/min, which is much lower than the case of only N2 plasma (43 Å/min).

Deposition of silicon oxycarbide (SiCOH) thin films by remote plasma atomic layer deposition was performed. In the experiment, the recipe was composed by adjusting the ratio of Ar and CH4 plasmas to control the carbon content in the SiCOH thin film. Octamethyl cyclotetrasiloxane was used as a precursor during the deposition process at 200, 300, and 400 °C. Ar plasma was used as an activant and CH4 plasma was used as a reactant. Plasma and deposition temperatures cause a significant impact on the physical and electrical properties of the film. When CH4 plasma was used during the deposition process, the film contained carbon and exhibited a low dielectric constant. In addition, when CH4 plasma is used as a reactant, Si–C bonds in the thin film form pores and lower ionic polarization to lower the dielectric constant. Fourier-transform infrared spectroscopy data indicate that the higher the ratio of CH4 plasma, the more the cage structure in the thin film. The cage structure contributes to lowering the dielectric constant of the thin film. The film deposited with Ar plasma has the dielectric constant of 3.2 and the film deposited with CH4 plasma has the dielectric constant of 2.6. In both plasma conditions, the dielectric constant was lower than the SiO2 film with the dielectric constant of 3.9. On the other hand, x-ray photoelectron spectroscopy analysis showed that SiO1–C3 and SiC4 bonds appeared in the film deposited with CH4 plasma, which did not appear in the film deposited with Ar plasma. These bonds affected the physical and electrical properties of the thin film.

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.