Supporting Information

Selecting for Surface-Induced vs Bulk Crystallization in P3HT Thin Films:

Distinct Morphology, Orientation, and Linear Growth Rates
Jesse Kuebler1, Sunil Dhapola1, Lucia Fernandez-Ballester1*
1
Department of Mechanical and Materials Engineering and Nebraska Center for Materials and
Nanoscience, University of Nebraska at Lincoln, Lincoln, Nebraska 68588, United States.
*Corresponding author: Email: [email protected]
238 °C 242 °C 243.5 °C 244.5 °C

Figure S1. Reflection polarized micrographs at Tiso = 238 °C (2 min), 242 °C (17.5 min), 243.5 °C (80 min),
and 244.5 °C (90 min). Scalebar is 100 µm.

Upon increasing the isothermal crystallization temperature (Tiso) above 240 °C, circulites formed with
progressively lower birefringence and increased splaying into extinct directions, hindering the ability to
distinguish the growth front and therefore impeding accurate measurement of the circulite radius
(compare Tiso = 238 °C and Tiso = 242 °C). Circulites nucleate and grow at Tiso = 243.5 °C, but no circulites
are observed after 90 min at Tiso = 244.5 °C, either due to negligible growth rate or to lack of nucleation.
Figure S2. (a) Polarized reflection micrographs of circulites growing during isothermal crystallization at 238
°C and (b) transmission micrographs of bulk objects growing during isothermal crystallization at 212 °C.
Scalebar is 50 µm. Note that the circulite nucleation density does not significantly vary within a sample or
across samples of the same thickness, but that of the BOs does.
 (a)
Normalized (100) Intensity (a.u.) 1 100nm
100 nmFS
(no cover) αi < αc
ai=0.08
100nm
100 (no cover) αi > αc
nmFS
100nm
100 nmCov
(coated)
100nm
100 nmCov
(coated
+ MC + MC)
40nm
40 nmCov
(coated
+ MC + MC)
Bulk
Bulk
0.5

0
0.3 0.35 0.4 0.45 0.5 0.55
q (Å-1)

(b) (c) Bulk

No cover Coated + MC
(d) αi = 0.14° (e) αi = 0.20°

1
αi = 0.08°
qz (Å-1)

0.5

0
0.6 0.3 0 0.3
qxy (Å-1)

Figure S3. (a) Normalized (100) I vs. q of 40 nm, 100 nm, and 100 µm (bulk) films with no cover (αi =
0.14° for entire film or αi = 0.08° for surface only) or Al coated (αi = 0.20°) films. (b) Ex-situ polarized
reflection optical micrographs of a coated + MC 100 nm film. Scalebar is 30 µm. (c) 2D transmission
diffraction pattern of a bulk (~100 µm thick) film. (d) GIWAXS pattern of 40 nm films with no cover or (e)
coated + MC.
 (a) (b)
No cover Cover
A0-1
2 237 °C 2 237 °C
229 °C 229 °C
Absorbance (a.u.)

Absorbance (a.u.)
216 °C 216 °C
A0-0
190 °C 187 °C
A0-1

1 1 A0-0

0 0
450 550 650 750 450 550 650 750
Wavelength (nm) Wavelength (nm)

(c) 0.4
233-231 °C (no cover)
207-205 °C (no cover)
198-196 °C (cover)
Δ(Absorbance) (a.u.)

A0-1

0.2 A0-0

0
450 550 650 750
Wavelength (nm)

Figure S4. UV-vis spectra at TC1,onset (red), TC1,endset (orange), TC2,onset (green), and TC2,endset (blue), for films
with (a) an uncovered and (b) a covered surface. (c) representative Δ(Absorbance) spectra of circulites,
underlayer, and BO (non-normalized version of Figure 8b in main paper). Note in (a) that the 229 °C
spectrum has significant amorphous contribution impeding fitting during circulite formation.
 (a) 150

Circulite
100 Impingement
W (meV)

50
200 nm
100 nm
40 nm
0
225 227 229 231 233 235
Temperature (°C)

Figure S5. (a) Zoomed in version on TC1 of Figure 8c in main paper. (b) Polarized reflection micrographs
during cooling showing circulite impingement at ~231 °C for all film thicknesses used.
 5
TM0 = 257 °C
4
Surface
Circulites
3

2
ln(G) (µm/min)

1 Bulk
0 Objects
10 µm
-1
200 nm
-2 100 nm
40 nm
-3 20 nm
-4
0 0.00005 0.0001 0.00015
1/TC(TM0-TC) (K-2)

Figure S6. Natural log of isothermal linear growth rates (ln(G)) of bulk objects (open shapes) and circulites
(filled shapes) in P3HT films with thickness of 10 µm (red circles), 200 nm (green squares), 100 nm (blue
diamonds), 40 nm (purple triangles), and 20 nm (grey crosses) plotted against 1/TC(TM0-TC) using TM0 = 257
°C.

Table S1 Kg values in K2
10 µm 200 nm 100 nm 40 nm
circulite 6.40E+04 5.33E+04 5.47E+04 5.73E+04
BO 2.32E+05 2.34E+05 4.03E+05 2.77E+05
BO/circ 3.627032 4.397053 7.376604 4.825491

Table S1. Extracted nucleation constant (Kg) for circulites and BOs and the Kg,BO / Kg,CIRCULITE ratio for 40 nm
- 10 μm thick films.
 (a) 0.03 (b) 0.03
After NI crystallization After ISO crystallization
(242 °C 30 min)
Free Surface

d(Absorbance)/dT (a.u.)
d(Absorbance)/dT (a.u.)

Covered
0.02 0.02
NIUND
NIUND
ISOCIR

0.01 NIBO 0.01

NICIR
NICIR

0 0
230 240 250 260 270 230 240 250 260 270
Temperature (°C) Temperature (°C)

Figure S7. Melting absorbance derivatives 570-640 nm (a) after non-isothermal (NI) crystallization of ~200
nm covered and uncovered films (heating rate of 10 °C/min) and (b) after isothermal (ISO) crystallization
at 242 °C for 30 min of a ~200 nm uncovered film (heating rate of 2 °C/min). Arrows point to the endset
melting temperatures (TM,END) of the underlayer, bulk objects, and circulites.

The non-isothermally crystallized covered film in Figure S7a exhibits one peak corresponding to the
melting of BOs (TM,END = 248.4 °C), while the uncovered film shows 2 peaks corresponding to melting of
the underlayer (TM,END = 245 °C) and of circulites (TM,END = 258 °C). In Figure S7b, TM,END =
245.5 °C corresponds to melting of the underlayer, and the higher temperature peaks correspond to
circulite melting: TM,END = 264.8 °C arises from melting of circulites formed at Tiso during the 30 min
isothermal step, while TM,END = 258 °C corresponds to melting of circulites formed non-isothermally during
cooling after the 30 min isothermal step.