Effect of Solvents, Their Mixture and Thermal Annealing on ...
Annealing with Different Solvents - NSRRC User Portal...
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Annealing with Different Solvents Solvent annealing chloroform toluene benzene DMF THF 1,4-dioxane O O O N O Solvents with oxygen (electronegative) Solvents without oxygen atom PS(20000)-b-P4VP(17000)(PDP) 1.0 C Cl Cl Cl H
Transcript of Annealing with Different Solvents - NSRRC User Portal...
Annealing with Different Solvents
Solvent annealing
chloroform
toluene
benzene
DMF
THF
1,4-dioxane
O
O O
N
O
Solvents with
oxygen (electronegative)
Solvents without
oxygen atom
PS(20000)-b-P4VP(17000)(PDP)1.0
C
ClClCl
H
Solvents without Oxygen Atom
chloroform
toluene
benzene
100 nm 500 nm
Height Phase
Film thickness: 41 nm
Film thickness: 42 nm
Film thickness: 50 nm
PS cylinders are perpendicular
to the surface when annealed
by the solvents without oxygen
atoms.
C
ClClCl
H
Solvents without Oxygen Atom
qz(Å
-1)
qy(Å-1)
qz(Å
-1)
qy(Å-1)
qz(Å
-1)
qy(Å-1)
chloroform
toluene
benzene Inte
nsity (
a.u
.)
0.200.150.100.050.00
q (Å-1
)
qz
qy
P4VP(PDP) Lamellae are parallel
to the surface.
3.8 nm
C
ClClCl
H
Solvents with Oxygen Atom
DMF
THF
1,4-dioxane
500 nm
Height Phase
100 nm
O
O O
N
O
Film thickness: 46 nm
Film thickness: 41 nm
Film thickness: 41 nm
PS cylinders are parallel to the
surface when annealed by the
solvents with oxygen atoms.
Solvents with Oxygen Atom
DMF
THF
1,4-dioxane
O
O O
N
O
Inte
nsity (
a.u
.)
0.200.150.100.050.00
q (Å-1
)
qz(Å
-1)
qy(Å-1)
qz(Å
-1)
qy(Å-1)
qz(Å
-1)
qy(Å-1)
qz
qy
P4VP(PDP) Lamellae are parallel
to the surface.
3.7 nm
33 nm
Reversibility
as-cast
chloroform THF
THF chloroform
O
O
C
ClClCl
H
The orientation of PS cylinders is reversible under alternating treatments by different solvents.
C
ClClCl
H
Solvent Effect on the Hydrogen Bonding
a
c
b d
i h, e
f
j
4.63ppm
5.26ppm
PDP in d-chloroform
PS-b-P4VP(PDP)1.0 in d-chloroform
N
H
O
b
m n
Solvent Effect on the Hydrogen Bonding
PDP in d-THF
PS-b-P4VP(PDP)1.0 in d-THF
a
c
b d h, e
f j i
7.97ppm
i
7.99ppm
O
N
H
O
b
m n
Solvent Effect on the Hydrogen Bonding
solvent PDP-OH chemical shift
PDP PS-b-P4VP(PDP)1.0
chloroform 4.63 5.26
benzene 4.10 4.47
toluene 3.89 4.30
THF 7.97 7.99
1,4-dioxane 7.43 7.44
DMF 9.37 9.39
The NMR peaks of PDP-OH shift
to higher frequency in the presence
of PS-b-P4VP.
The NMR peaks of PDP-OH are at
higher frequency and no significant
change in the presence of PS-b-
P4VP.
C
ClClCl
O
O O
N
O
Solvent Effect on the Morphology
N
H
O
b
m n
O
O O
N
O
DMF
THF
1,4-dioxane
PDP molecules are unbound during annealing in
the vapor of the solvents with oxygen atoms.
The strength of H-bonding between 4VP and
PDP is weakened due to the competition of
oxygen atoms on solvent molecules.
The PS cylinders tend to be parallel due to the
favorable P4VP-substrate interactions.
Conclusions
Two simple approaches are found to be useful for controlling the microdomain
orientation in block copolymer-based supramolecular thin films:
Adjusting the grafting density of small molecules incorporated in block
copolymers. The arrangements of small molecules determine the orientation of
microdomains.
Annealing thin films under vapors of different solvents. The strength of
hydrogen bonding interaction between PDP and P4VP is the key for the
orientation control.
Acknowledgements
Acknowledgements
Mr. Chih-Hung Lee, Mr. Wei-Han Huang and Mr. Po-Yu Chen
Dr. U-Ser Jeng and Dr. Chun-Jen Su
NSRRC for SAXS and GISAXS Measurements
Grants from Taiwan National Science Council
qz(Å
-1)
qy(Å-1)
GISAXS Patterns
Solvents
toluene benzene chloroform THF 1,4-dioxane DMF
Solubility parameter (MPa1/2) 18.2 18.8 19.0 18.6 20.5 24.8
Boiling point (°C) 111 80 61 66 102 153
Resulting orientation ⊥ ⊥ ⊥ ∥ ∥ ∥
d-spacing of PS cylinders (nm) 35.3
0.0178
35.3
0.0178
35.7
0.0176
33.6
0.0187
34.7
0.0181
32.1
0.0196
d-spacing of P4VP(PDP)
lamella (nm)
3.9
0.161
3.9
0.161
3.7
0.169
3.8
0.165
3.7
0.170
3.9
0.161
C
ClClCl
O
O ON
O
