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.

Facile synthesis of an organic/inorganic hybrid 2D structure tincone film by molecular layer deposition.

Organic/inorganic hybrid tincone films were deposited by molecular layer deposition (MLD) using N,N'-tert-butyl-1,1-dimethylethylenediamine stannylene(II) as a precursor and hydroquinone (HQ) as an organic reactant. From previous studies it is known that SnO can be fabricated through a reaction with H2O, which has low oxidizing power. Similarly, when combined with HQ having a bi-functional hydroxyl group, SnO-based 2D hybrid tincones can be produced. In most aromatic ring-based metalcones described in previous studies, graphitization by pyrolysis occurred during post-annealing. In this study of tincones fabricated with a divalent precursor after a vacuum post-annealing process, the structural rearrangement of the SnO and the benzene ring bonds proceeded to form a SnO-based hybrid 2D structure. The rearrangement of the resulting structure occurred through π-π stacking (without pyrolysis) of the benzene ring. To understand the mechanism of fabrication of 2D hybrid tincones by π-π stacking of the benzene ring and the increase of the crystallinity of SnO after the annealing process, the structural rearrangement was observed using X-ray photoelectron spectroscopy (XPS), grazing incidence X-ray diffraction (GIXRD), grazing-incidence wide-angle X-ray scattering (GIWAXS), and Raman spectroscopy. Thereafter, the design of the crystal structure was investigated.

Dry-Etchable Molecular Layer-Deposited Inhibitor Using Annealed Indicone Film for Nanoscale Area-Selective Deposition.

In semiconductor production, the technology node of a device is becoming extremely small below 5 nm. Area selective deposition (ASD) is a promising technique for creating improved overlay or self-alignment, remedying a conventional top-down method. However, the conventional materials and process (self-assembled monolayer, polymer and carbon film fabricated by chemical vapor deposition, and spin coating) for ASD are not suitable for highly conformal deposition. Thus, we investigated a new strategy to deposit conformal films in ASD by molecular layer deposition (MLD). The MLD processes were conducted for an indicone film deposited by INCA-1 (bis(trimethysily)amidodiethyl indium) and hydroquinone (HQ), as well as an alucone film deposited by TMA (trimethylaluminum) and HQ. After thermal heat treatment of the MLD films, variations in thickness, refractive index, and constituent elements of the annealed MLD films were investigated. The indicone film was used as an inhibiting layer for ASD and was etchable with a dry-etching process. The reactive ion etching process on annealed indicone film was optimized according to plasma power, gas concentration, and working pressure. Ruthenium (Ru) ALD was then performed on the annealed MLD films to investigate nucleation delaying cycles and inhibiting properties. A patterned substrate with an MLD/Si line was created via the RIE process, which was allowed to observe the selectivity of the annealed MLD films. In addition, a patterned substrate of SiO2/annealed indicone/Mo was used to investigate the Ru-selective ALD at the nanoscale. The Ru thin film was selectively deposited on the Mo side-wall surface of a 3D trench structure. The growth of the Ru film was inhibited selectively on an annealed indicone surface of approximately 5 nm.

Facile rearrangement of molecular layer deposited metalcone thin films by electron beam irradiation for area selective atomic layer deposition.

Area selective atomic layer deposition (AS-ALD) is a promising future technology for the realization of a 5 nm scale Si complementary field effect transistor (FET) and its application in industry. AS-ALD is one of the "bottom-up" technologies, which is a key process that can reduce the cost of fabrication and decrease positional error as an alternative to the conventional "top down" technology. We researched an inhibitor for AS-ALD using molecular layer deposited (MLD) films annealed by electron beam irradiation (EBI). We studied the effect of EBI on an indicone film that was fabricated by using bis(trimethylsilyl)amidodiethyl indium (INCA-1), hydroquinone (HQ), an alucone film fabricated by using trimethylaluminum (TMA) and 4-mercaptophenol (4MP). The EBI effect on MLD films was evaluated by investigating the changes in thickness, composition and structure. In order to observe the selectivity of the annealed indicone film, atomic layer deposition of ZnO was performed on the annealed indicone/silicon line pattern, and it was found that the surface of annealed indicone can inhibit ALD of ZnO for 20 cycles as compared to a Si surface.

Thermal Annealing of Molecular Layer-Deposited Indicone Toward Area-Selective Atomic Layer Deposition.

Area-selective atomic layer deposition (AS-ALD) is a promising technique for fine nanoscale patterning, which may overcome the drawbacks of conventional top-down approaches for the fabrication of future electronic devices. However, conventional materials and processes often employed for AS-ALD are inadequate for conformal and rapid processing. We introduce a new strategy for AS-ALD based on molecular layer deposition (MLD) that is compatible with large-scale manufacturing. Conformal thin films of "indicone" (indium alkoxide polymer) are fabricated by MLD using INCA-1 (bis(trimethylsily)amidodiethylindium) and HQ (hydroquinone). Then, the MLD indicone films are annealed by a thermal heat treatment under vacuum. The properties of the indicone thin films with different annealing temperatures were measured with multiple optical, physical, and chemical techniques. Interestingly, a nearly complete removal of indium from the film was observed upon annealing to ca. 450 °C and above. The chemical mechanism of the thermal transformation of the indicone film was investigated by density functional theory calculations. Then, the annealed indicone thin films were applied as an inhibiting layer for the subsequent ALD of ZnO, where the deposition of approximately 20 ALD cycles (equivalent to a thickness of approximately 4 nm) of ZnO was successfully inhibited. Finally, patterns of annealed MLD indicone/Si substrates were created on which the area-selective deposition of ZnO was demonstrated.