Fluorine-containing silicon compounds, silicone resins, resist compositions, and patterning process
Fluorine-containing silicon compounds having the general formula (1): wherein X 1 , X 2 , and X 3 each are hydrogen, hydroxyl, halogen, a straight, branched or cyclic alkoxy group of 1 to 6 carbon atoms, or a monovalent organic group of 1 to 20 carbon atoms having a straight, branched, cyclic or polycyclic skeleton, Y is a divalent organic group, R 1 and R 2 are each independently hydrogen or a monovalent organic group of 1 to 20 carbon atoms having a straight, branched, cyclic or polycyclic skeleton, or R 1 and R 2 may bond together to form a ring with the carbon atom to which they are attached silicone resins obtained from the compounds of formula (1) has an appropriate acidity to enable formation of a finer pattern while minimizing the pattern collapse by swelling when used in a resist composition.
1. A fluorine-containing silicon compound having the general formula (1):
wherein X 1 , X 2 , and X 3 each are hydrogen, hydroxyl, halogen, a straight, branched or cyclic alkoxy group of 1 to 6 carbon atoms, or a monovalent organic group of 1 to 20 carbon atoms having a straight, branched, cyclic or polycyclic skeleton, Y is a divalent organic group, R 1 and R 2 are each independently hydrogen or a monovalent organic group of 1 to 20 carbon atoms having a straight, branched, cyclic or polycyclic skeleton, or R 1 and R 2 may bond together to form a ring with the carbon atom to which they are attached.
2. The fluorine-containing silicon compound of claim 1 , wherein Y in formula (1) is a divalent alicyclic organic group.
3. A fluorine-containing silicon compound having the general formula (2):
wherein X 1 , X 2 , and X 3 each are hydrogen, hydroxyl, halogen, a straight, branched or cyclic alkoxy group of 1 to 6 carbon atoms, or a monovalent organic group of 1 to 20 carbon atoms having a straight, branched, cyclic or polycyclic skeleton, R 1 and R 2 are each independently hydrogen or a monovalent organic group of 1 to 20 carbon atoms having a straight, branched, cyclic or polycyclic skeleton, or R 1 and R 2 may bond together to form a ring with the carbon atom to which they are attached, W 1 and W 2 are each independently methylene or oxygen, R 6 is hydrogen, methyl, fluorine or trifluoromethyl, p is 0 or 1, and q is 0 or 1.
4. A fluorinated silicone resin comprising recurring units having the general formula (1a) or (2a):
wherein at least one of X 1a , X 2a , and X 3a is an oxygen atom and the remaining are hydrogen, hydroxyl, halogen, a straight, branched or cyclic alkoxy group of 1 to 6 carbon atoms, or a monovalent organic group of 1 to 20 carbon atoms having a straight, branched, cyclic or polycyclic skeleton,
Y is a divalent organic group,
R 1 and R 2 are each independently hydrogen or a monovalent organic group of 1 to 20 carbon atoms having a straight, branched, cyclic or polycyclic skeleton, or R 1 and R 2 may bond together to form a ring with the carbon atom to which they are attached,
W 1 and W 2 are each independently methylene or oxygen,
R 6 is hydrogen, methyl, fluorine or trifluoromethyl,
p is 0 or 1, and q is 0 or 1.
5. A resist composition comprising
(A) the silicone resin of claim 4 ,
(B) a photoacid generator, and
(C) an organic solvent.
6. A patterning process comprising the steps of:
applying the resist composition of claim 5 onto a substrate to form a resist layer,
heat treating the resist layer and exposing it to high energy radiation having a wavelength of up to 300 nm or electron beam through a photomask, and
optionally heat treating the exposed resist layer, and developing it with a developer.