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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

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