We investigated the resistance of a low-k SiOCH film structure to plasma-irradiation damage by comparing films deposited by neutral-beam enhanced chemical-vapour-deposition (NBECVD) and conventional plasma CVD techniques to clarify the degradation mechanism of the dielectric constant in low dielectric SiOCH film during plasma etching. We found that the durability of a low-k SiOCH film structure to plasma irradiation strongly depended on the kind of Si–O structure the film had. In particular, a linear Si–O structure was less affected by plasma exposure than were network/cage Si–O structures because of the small amount of stress in the O–Si–O structure. In addition, this linear Si–O structure helped to reduce the number of methyl groups removed from the film by plasma irradiation, which preserved the dielectric constant. Since the NBECVD technique can generate a low-k SiOCH film with more linear Si–O structures than conventional plasma CVD, a film made through this technique has very strong plasma durability.

To precisely control the dielectric constant and the structure of a low-k SiOC film, we have developed a neutral-beam-enhanced chemical vapour deposition (NBECVD) method. Using Ar NBECVD, we can precisely control the dielectric constant and the film modulus of low-k SiOC deposited on Si substrates because this method avoids precursor dissociation that results from electron collisions and UV photons in plasma. Optimizing the ratio between Si–O and Si–(CH3)x as well as the proportions of linear (two-dimensional SiOC), network and cage (three-dimensional SiOC) structures by changing the precursor, we obtained a k value of 2.2 and a reasonable modulus by using dimethyl dimethoxy silane as a precursor. Additionally, the NBECVD process is applicable as a method for damage-free super-low-k film deposition on the underlying low-k film that is sensitive to damage by the plasma.

We developed a neutral-beam-enhanced method of chemical vapour deposition (NBECVD) to obtain a lower dielectric constant for the SiOCH interlayer dielectric film while maintaining a reasonable modulus. We achieved a higher deposition rate than that with the precursor of dimethyl-dimethoxy-silane (DMDMOS) we previously reported on by using Ar NBECVD with a precursor of dimethoxy-tetramethyl-disiloxine (DMOTMDS). This is because of the high absorption coefficient of DMOTMDS. Ar NBECVD with DMOTMDS also achieved a much lower dielectric constant than the conventional PECVD film, because this method avoids the precursor dissociation that causes low dielectric film with many linear Si–O structures. We obtained a k value of 1.9 for the super-low-k SiOCH film with an extremely water resistant, and very thermally stable and integration-possible modulus (>4 GPa) by controlling the bias power.

Ar neutral beam enhanced chemical vapor deposition can control the dielectric constant and film modulus of low-k SiOC deposited on Si substrates precisely because it avoids precursor dissociation due to electron collisions and UV photons in plasma. Optimizing the ratio between Si-O and Si-(CH 3 ) x as well as the proportions of linear, network, and cage Si-O structures by changing the precursor, we obtained a k of 2.2 and a reasonable modulus by using either dimethyl diethoxy silane or dimethyl dimethoxy silane as a precursor.

We investigated a pulse-time-modulated neutral-beam-enhanced CVD at a low substrate temperature of -70 o C with dimethoxy-tetramethyl-disiloxane to form low-k SiOCH film. This method provided an ultimate low-k SiOCH film with a k-value of 1.3, a sufficient modulus of more than 5 GPa, and ultra-high thermal stability (no desorption of CH 3 and H 2 O by 400 o C annealing). This result is explained by the extremely high polymerization due to a drastic increase in absorption probability of the precursor combined with the pulse-time-modulated neutral beam irradiation and low substrate temperature of -70 o C.