No abstract

Tin monosulfide (SnS) is a promising p-type semiconductor material for energy devices. To realize the device application of SnS, studies on process improvement and film characteristics of SnS is needed. Thus, we developed a new film process using atomic layer deposition (ALD) to produce SnS films with high quality and various film characteristics. First, a process for obtaining a thick SnS film was studied. An amorphous SnS2 (a-SnS2) film with a high growth rate was deposited by ALD, and a thick SnS film was obtained using phase transition of a-SnS2 film by vacuum annealing. Subsequently, we investigated the effect of seed layer on formation of SnS film to verify the applicability of SnS to various devices. Separately deposited crystalline SnS and SnS2 thin films were used as seed layer. The SnS film with a SnS seed showed small grain size and high film density from the low surface energy of the SnS seed. In the case of the SnS film using a SnS2 seed, volume expansion occurred by vertically grown SnS grains due to a lattice mismatch with the SnS2 seed. The obtained SnS film using the SnS2 seed exhibited a large reactive site suitable for ion exchange.

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.

Changes in the thin film properties of SiNx deposited via atomic layer deposition using remote N2 plasma were investigated based on the frequency of adding a hydrogen (H2) plasma treatment step during the process. The deposition rate decreased from 0.36 to 0.32 A/cycle when compared to SiNx deposited through the conventional deposition process for a thin film that was subjected to H2 treatment processes every 10th cycle, every 5th cycle, and every single cycle of SiNx deposition compared to the deposition process without H2 plasma at a temperature of 400°C. As the hydrogen treatment process increased beyond a 5:1 ratio, the hydrogen content in the thin film increased based on secondary ion mass spectroscopy analysis, and a change in binding energy state was shown via X-ray photoelectron spectroscopy. The thin film deposited using the hydrogen plasma treatment process at a ratio of 10:1 showed similar characteristics to the SiNx thin film deposited through the conventional atomic layer deposition process and showed excellent etch resistance without an increase in the etch rate. The step coverage characteristics were increased by 16% compared to the deposition process without a H2 plasma treatment process.