Synthesis of low-k SiONC thin films by plasma-assisted molecular layer deposition with tetraisocyanatesilane and phloroglucinol.

Low-k SiONC thin films with excellent thermal stabilities were deposited using plasma-assisted molecular layer deposition (PA-MLD) with a tetraisocyanatesilane (Si(NCO)4) precursor, N2plasma, and phloroglucinol (C6H3(OH)3). By adjusting the order of the N2plasma exposure steps within the PA-MLD process, we successfully developed a deposition technique that allows accurate control of thickness at the Ångström level via self-limiting reactions. The thicknesses of the thin films were measured through spectroscopic ellipsometry (SE). By tuning the N2plasma power, we facilitated the formation of -NH2sites for phloroglucinol adsorption, achieving a growth per cycle of 0.18 Å cycle-1with 300 W of N2plasma power. Consequently, the thickness of the films increased linearly with each additional cycle. Moreover, the organic linkers within the film formed stable bonds through surface reactions, resulting in a negligible decrease in thickness of approximately -11% even upon exposure to a high annealing temperature of 600 °C. This observation was confirmed by SE, distinguishing the as-prepared film from previously reported low-k films that fail to maintain their thickness under similar conditions. X-ray photoelectron spectroscopy (XPS) and current-voltage (I-V) and capacitance-voltage (C-V) measurement were conducted to evaluate the composition, insulating properties, and dielectric constant according to the deposition and annealing conditions. XPS results revealed that as the plasma power increased from 200 to 300 W, the C/Si ratio increased from 0.37 to 0.67, decreasing the dielectric constant from 3.46 to 3.12. Furthermore, there was no significant difference in the composition before and after annealing, and the hysteresis decreased from 0.58 to 0.19 V owing to defect healing, while maintaining the leakage current density, breakdown field, and dielectric constant. The low dielectric constant, accurate thickness control, and excellent thermal stability of this MLD SiONC thin film enable its application as an interlayer dielectric in back-end-of-line process.

Water vapor and hydrogen gas diffusion barrier characteristics of Al2O3-alucone multi-layer structures for flexible OLED display applications.

Organic light emitting diodes (OLEDs) and amorphous oxide semiconductors (AOSs), which are very important technologies in high performance flexible displays, have issues related to degradation due to diffusion of water and hydrogen, respectively. To solve these issues, gas diffusion barrier properties were evaluated with aluminum oxide deposited by atomic layer deposition (ALD) and alucone deposited by molecular layer deposition (MLD) using trimethylaluminum (TMA) as a metal precursor and H2O and hydroquinone (HQ) as co-reactants, respectively. The water vapor transmission rate (WVTR) and hydrogen gas permeability (HGP) were measured for the fabricated films via electrical calcium tests and vacuum time-lag, respectively. To enhance the diffusion barrier properties, Al2O3/alucone hybrid multi-layer structures were successfully deposited through an in situ ALD/MLD process. The 4.5 dyads of the Al2O3/alucone structure showed improved barrier properties compared to the single Al2O3 film with a WVTR of 8.24 × 10-5 g m-2 day-1 and a HGP of 9.93 × 10-5 barrer, and factors related to gas diffusion in multi-layer structures were discussed. The stability to external stress was also evaluated based on the WVTR change rate after the bending test, and we confirmed that the stability of the multi-layer structures was improved due to the flexibility of inserted alucone layers. All the developed structures had a high optical transmittance of >80% in the 300-800 nm wavelength region based on UV-vis measurements.

Atomic-Layer-Deposited SiOx/SnOx Nanolaminate Structure for Moisture and Hydrogen Gas Diffusion Barriers.

High-density SnOx and SiOx thin films were deposited via atomic layer deposition (ALD) at low temperatures (100 °C) using tetrakis(dimethylamino)tin(IV) (TDMASn) and di-isopropylaminosilane (DIPAS) as precursors and hydrogen peroxide (H2O2) and O2 plasma as reactants, respectively. The thin-film encapsulation (TFE) properties of SnOx and SiOx were demonstrated with thickness dependence measurements of the water vapor transmission rate (WVTR) evaluated at 50 °C and 90% relative humidity, and different TFE performance tendencies were observed between thermal and plasma ALD SnOx. The film density, crystallinity, and pinholes formed in the SnOx film appeared to be closely related to the diffusion barrier properties of the film. Based on the above results, a nanolaminate (NL) structure consisting of SiOx and SnOx deposited using plasma-enhanced ALD was measured using WVTR (H2O molecule diffusion) at 2.43 × 10-5 g/m2 day with a 10/10 nm NL structure and time-lag gas permeation measurement (H2 gas diffusion) for applications as passivation layers in various electronic devices.