Thermal kinetics of free volume in porous spin-on dielectrics: exploring the network- and pore-properties


Thermal kinetics of free volume in porous spin-on dielectrics: exploring the network- and pore-properties

Elsherif, A. G. A.; Koehler, N.; Liedke, M. O.; Butterling, M.; Hirschmann, E.; Ecke, R.; Schulz, S. E.; Wagner, A.

Comprehensive ex-situ and in-situ investigations of thermal curing processes in spin-on ultra-low-k thin films conducted by positron annihilation spectroscopy and Fourier transform infrared spectroscopies are presented. Positron annihilation lifetime spectroscopy of ex-situ cured samples reveals an onset of the curing process at about 200 °C, which advances with increasing curing temperature. Porogen agglomeration followed by diffusive migration to the surface during the curing process leads to the generation of narrow channels across the film thickness. The size of those channels is determined by a pore size distribution analysis of positron lifetime data. Defect kinetics during in-situ thermal curing has been investigated by means of Doppler broadening spectroscopy of the annihilation radiation, showing several distinct partially superposed and subsequent curing stages, i.e., moisture and residual organic solvents removal, SiOx network cross-linking, porogen decomposition, and finally creation of a stable porous structure containing micropore channels interconnecting larger mesopores formed likely due to micelle like interaction between porogen molecules, for curing temperatures not larger than 500 °C. Static (sequencing curing) states captured at specific temperature steps confirm the conclusions drawn during the dynamic (continuous curing) measurements. Moreover, the onset of pore inter-connectivity is precisely estimated as pore interconnectivity sets in at 380–400 °C.

Keywords: In-situ curing; Positron annihilation spectroscopy; Porogen removal; Porosimetry; FTIR; Dielectrics; Pore size distribution; Positronium

Related publications

Permalink: https://www.hzdr.de/publications/Publ-31402
Publ.-Id: 31402