Supporting Information
Ultralow-Threshold Up-Converted Lasing in Oligofluorenes with
Tailored Strong Nonlinear Absorption
Burak Guzelturk1,#, Alexander L. Kanibolotsky2,3,#, Clara Orofino-Pena2, Nicolas Laurand4,
Martin D. Dawson4, Peter J. Skabara2,*, and Hilmi Volkan Demir1,5,*
1
Department of Electrical and Electronics Engineering, Department of Physics, UNAM -
Institute of Materials Science and Nanotechnology, Bilkent University, Ankara 06800 Turkey
2
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Thomas
Graham Building, 295 Cathedral Street, Glasgow G1 1XL, UK
3 Institute of Physical-Organic Chemistry and Coal Chemistry, 02160 Kyiv, Ukraine
4
Institute of Photonics, University of Strathclyde, Glasgow G4 0NW, UK
5
Luminous! Center of Excellence for Semiconductor Lighting and Displays, School of Electrical
and Electronic Engineering, School of Physical and Mathematical Sciences, Nanyang
Technological University, Nanyang Avenue, Singapore 639798, Singapore
# These authors contributed equally to this work
*To whom correspondence should be addressed: volkan@bilkent.edu.tr, hvdemir@ntu.edu.sg
(H.V.D), peter.skabara@strath.ac.uk (P.S)
2.138
2.066
2.277
0.988
0.973
0.963
0.861
0.837
0.820
0.810
0.804
0.799
0.791
0.783
0.773
0.765
0.675
0.659
0.641
1.100
1.093
1.152
7.907
7.887
7.868
7.862
7.858
7.849
7.843
7.830
7.823
7.809
7.797
7.790
7.762
7.743
7.741
7.714
7.689
7.681
7.658
7.638
7.391
7.379
7.372
7.365
7.347
7.342
7.338
7.323
7.306
7.303
7.260
8.533
3.109
Person 7-1
AK396R
10.7 mg
8.6
8.4
8.2
8.0
7.8
7.6
NAME
EXPNO
PROCNO
Date_
Time
INSTRUM
PROBHD
PULPROG
TD
SOLVENT
NS
DS
SWH
FIDRES
AQ
RG
DW
DE
TE
D1
TD0
ppm
7.4
ppm
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
36.000
3.0
2.5
2.0
1.5
1.0
ppm
154.381
7.5
25.817
8.0
1.883
8.5
usec
usec
K
sec
ppm
0.8
3.035
9.0
0.899
9.5
1.0
Hz
Hz
sec
======== CHANNEL f1 ========
NUC1
1H
P1
9.40 usec
PL1
-4.00 dB
PL1W
19.93825150 W
SFO1
400.1324710 MHz
SI
32768
SF
400.1300098 MHz
WDW
EM
SSB
0
LB
0.30 Hz
GB
0
PC
1.00
ppm
1.2
D211990
1
1
20141013
12.45
spect
5 mm QNP 1H/13
zg30
32564
CDCl3
64
2
8223.685
0.252539
1.9799412
181
60.800
6.50
300.0
2.00000000
1
Figure S1. 1H NMR of T6
31.094
30.986
29.196
23.378
22.108
22.073
21.867
13.537
13.454
39.890
54.861
54.691
NAME
EXPNO
PROCNO
Date_
Time
INSTRUM
PROBHD
PULPROG
TD
SOLVENT
NS
DS
SWH
FIDRES
AQ
RG
DW
DE
TE
D1
D11
TD0
122.441
121.059
119.494
119.227
125.684
76.836
76.518
76.201
125.684
122.441
121.059
119.494
119.227
140.324
140.078
139.855
139.550
140.324
140.078
139.855
139.550
153.971
151.340
150.996
150.535
153.971
151.340
150.996
150.535
Person 7-1
AK396R
31.2 mg
D212002
1
1
20141013
14.50
spect
5 mm QNP 1H/13
zgpg30
16384
CDCl3
1024
4
22058.824
1.346364
0.3714207
2050
22.667
6.50
300.0
0.69999999
0.03000000
1
Hz
Hz
sec
usec
usec
K
sec
sec
======== CHANNEL f1 ========
NUC1
13C
P1
7.00 usec
PL1
-2.60 dB
PL1W
61.34123230 W
SFO1
100.6228298 MHz
150
160
150
140
140
130
ppm
130
120
110
======== CHANNEL f2 ========
CPDPRG2
waltz16
NUC2
1H
PCPD2
80.00 usec
PL2
-4.00 dB
PL12
14.06 dB
PL13
120.00 dB
PL2W
19.93825150 W
PL12W
0.31166428 W
PL13W
0.00000000 W
SFO2
400.1316005 MHz
SI
32768
SF
100.6128193 MHz
WDW
EM
SSB
0
LB
1.00 Hz
GB
0
PC
1.40
100
90
80
70
60
50
40
30
20
10
ppm
Figure S2. 13C NMR of T6
0
50
100
150
200
250
436
100
Heat Flow, W/g
Weight, %
90
80
106
70
60
50
50
100
150
200
250
300
350
400
450
500
550
600
o
Temperature, C
Figure S3. Thermogravimetric (solid line) and DSC (dashed line) analyses of T6 measured at 10 oC/min.
The temperature corresponding to 5% mass loss and the glass transition are shown.
Figure S4. PL and absorbance spectra of T3, T4 and T6 molecules in their solid-films.
Figure S5. PL decay curves of the T3, T4 and T6 measured at the 0-0 transition peak with 1/e lifetimes of
0.85, 1.14 and 0.78 ns, respectively.
Figure S6. (a) Emission spectra on quartz of the T6 molecules as the pump intensity is increased. 1PA
pumped ASE in T6 is clearly visible with an emerging narrow peak at 448 nm. The inset shows the
change of the FWHM emission as a function of the pump intensity. (b) Pump intensity vs integrated
emission intensity measurement under 1PA pumping in T6 molecules giving 1.43 µJ/cm2 threshold.
We have measured the extinction coefficients of the truxene oligomers at their peak absorption
wavelengths as follows:
 = 411000 l mol–1 cm–1 for T3 (Ref. 1)
 = 473000 l mol–1 cm–1 for T4 (Ref. 1)
 = 680000 l mol–1 cm–1 for T6
For this, we used T3, T4 and T6 solutions (in toluene) at 3.76 10-6, 6.52 10-7 and 2.63 10-6 mol/L
concentrations, respectively.
Table S1. Comparison of the experimental conditions for the frequency up-converted laser thresholds in
the organic semiconductors.
Reference
This work
Ref.
2
Ref. 3
Ref. 4
Ref. 5
Material
Truxene based star-shaped
oligofluorenes with 6 fluorene
units per arm (T6)
Ladder-type poly(p-phenylene)
(MeLPPP)
Polyfluorene (PFO)
Bisfluorene dendrimer (BPCz)
1,4-bis[2-[4-[N,N-di(ptotyl)amino]phenyl]vinyl]benzene
(DADSB)
Threshold
3.1 mJ/cm2
>200
mJ/cm2
42 mJ/cm2
4.9 mJ/cm2
4.5 mJ/cm2
Pulse
duration
120 fs
Repetition
rate
1 kHz
Excitation
geometry
spot
Spot
size
1.48
mm
Medium
Threshold
1 bar
(ambient)
3.1 mJ/cm2
150 fs
1 kHz
spot
NA
10-4 mbar
100 fs
100 fs
150 fs
NA
5 kHz
1 kHz
NA
spot
spot
NA
85 µm
1 mm
NA
10-4 mbar
1 bar
(ambient)
>200
mJ/cm2
42 mJ/cm2
4.9 mJ/cm2
4.5 mJ/cm2
1
A. L. Kanibolotsky, R. Berridge, P. J. Skabara, I. F. Perepichka, D. D. C. Bradley and M.
Koeberg, J. Am. Chem. Soc., 2004, 126, 13695–702.
2
C. Bauer, B. Schnabel, E.-B. Kley, U. Scherf, H. Giessen and R. F. Mahrt, Adv. Mater.,
2002, 14, 673–676.
3
G. Tsiminis, A. Ruseckas, I. D. W. Samuel and G. a. Turnbull, Appl. Phys. Lett., 2009, 94,
253304.
4
G. Tsiminis, J.-C. Ribierre, A. Ruseckas, H. S. Barcena, G. J. Richards, G. A. Turnbull, P.
L. Burn and I. D. W. Samuel, Adv. Mater., 2008, 20, 1940–1944.
5
H.-H. Fang, S.-Y. Lu, X.-P. Zhan, J. Feng, Q.-D. Chen, H.-Y. Wang, X.-Y. Liu and H.-B.
Sun, Org. Electron., 2013, 14, 762–767.