Pulsed IR laser-induced ablation of bulk poly[oxy(tetramethyldisilane-1,2-diyl)], [(CH 3 ) 2 -Si(CH 3 ) 2 SiO] n ,yields thin polyoxocarbosilane films whose polymeric structure consists of a backbone composed of -(CH 3 ) 2 Si(CH 3 ) 2 SiO-and -O(CH 3 ) 2 SiO-units, which is cross-linked via SiSiC 2 O, C 3 SiO, C 2 SiHO, CSiHO 2 , and CSiO 3 moieties. These laser-fabricated hybrides of siloxanes and polysilylenes are insoluble in organic solvents and thermally superior to siloxanes and polysilylenes, which makes them intriguing for applications in thermally exposed devices.
Gas-phase photolysis of methyldisiloxanes [(CH3)
n
H3
-
n
Si]2O (n = 1−3) has been achieved
for the first time through absorption of ArF laser radiation at 193 nm and has been shown
to yield C1−C2 hydrocarbons (major volatile products), methylsilanes (minor volatile
products), and solid methylsilicones with their H(Si) content and Si/O ratio reflecting those
of the parent compounds. The identified volatile and solid products are compatible with a
number of reactions occurring within less than 1 ms in a narrow region of the gaseous sample
maintained at room temperature. These reactions are discussed. The solid deposited materials
were characterized by FTIR, NMR, UV, and XP spectroscopy, electron microscopy, and
thermal gravimetry. They were revealed to contain all possible SiC
x
H
y
O
z
(x + y + z = 4)
compositions, to possess nanometer-sized texture, and to be thermally more stable than linear
poly(dialkylsiloxanes).
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