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MimiBTIBDT DIO SI 20181017 - Royal Society of Chemistry · exciton absorption and ground state...
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S1 Supporting Information Effects of 1,8-Diiodooctane on Domain Nanostructure and Charge Separation Dynamics in PC 71 BM-Based Bulk Heterojunction Solar Cells Sylvia J. Lou, 1 Nanjia Zhou, 2 Xugang Guo, 1,3 Robert P. H. Chang, 2* Tobin J. Marks, 1,2 * Lin X. Chen 1,4 * Affiliations 1 Department of Chemistry and the Argonne-Northwestern Solar Energy Research Center, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States 2 Department of Materials Science and Engineering and the Argonne-Northwestern Solar Energy Research Center, Northwestern University, Evanston, Illinois 60208, United States 3 Department of Materials Science and Engineering, South University of Science and Technology of China, No. 1088, Xueyuan Blvd, Shenzhen, Guangdong, 518055, China 4 Chemical Sciences and Engineering Division, Argonne National Laboratory, Darien, Illinois 60439, United States Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A. This journal is © The Royal Society of Chemistry 2018
Transcript of MimiBTIBDT DIO SI 20181017 - Royal Society of Chemistry · exciton absorption and ground state...
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Supporting Information
Effects of 1,8-Diiodooctane on Domain Nanostructure and Charge Separation
Dynamics in PC71BM-Based Bulk Heterojunction Solar Cells
Sylvia J. Lou,1 Nanjia Zhou,2 Xugang Guo,1,3 Robert P. H. Chang,2* Tobin J. Marks,1,2*
Lin X. Chen1,4*
Affiliations
1 Department of Chemistry and the Argonne-Northwestern Solar Energy Research
Center, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208,
United States 2 Department of Materials Science and Engineering and the Argonne-Northwestern
Solar Energy Research Center, Northwestern University, Evanston, Illinois 60208,
United States 3 Department of Materials Science and Engineering, South University of Science and
Technology of China, No. 1088, Xueyuan Blvd, Shenzhen, Guangdong, 518055, China 4 Chemical Sciences and Engineering Division, Argonne National Laboratory, Darien,
Illinois 60439, United States
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is © The Royal Society of Chemistry 2018
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Solar cell external quantum efficiency data
Figure S1. External quantum efficiencies of PBTIBDT:PCBM solar cells with 0-5 vol% DIO added to the active layer solution Small angle x-ray scattering component fits forPBTIBDT+PCBM solutions with 0-5 vol% DIO
Figure S2. Representative fits of PBTIBDT+PCBM solution data with 0 vol% DIO
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0
EQE
(%)
800700600500400300Wavelength (nm)
0%DIO 1%DIO 2%DIO 3%DIO 4%DIO 5%DIO
0.01
2
46
0.1
2
46
1
2
∆OD
(a.u
.)
7 80.01
2 3 4 5 6 7 80.1
2 3 4
Q (Å-1)
BTIBDT:PCBM 0%DIO fit BTIBDT:PCBM 0%DIO BTIBDT 0%DIO PCBM 0%DIO
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Table S1. Table of small angle x-ray scattering component fit percentages GIWAXS data analysis procedures and 2D images
Figure S3. 2D GIWAXS images of neat films of a) PBTIBDT 0% DIO and b) PCBM and blend PBTIBDT:PCBM films with: c) 0 vol % DIO, d) 3 vol% DIO, e) 5vol% DIO. Linecuts were taken parallel to the horizontal (qxy) and vertical (qz) axes to approximate the in-plane and out-of-plane structure of the polymer, respectively (Figure S4). The
[DIO] (vol%) Percentage of each component
PCBM PBTIBDT
0 6 94 1 5 95 2 5 95 3 3 97 4 4 96 5 4 96
a) b) 2.0
1.5
1.0
0.5
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q z (
Å-1
)
2.01.51.00.50.0qxy (Å-1)
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Å-1
)
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2.01.51.00.50.0qxy (Å-1)
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Å-1
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2.01.51.00.50.0qxy (Å-1)
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-100x10-3 0 100
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-100x10-3 0 100
qxy (Å-1
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q z (
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-100x10-3 0 100
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c) d) e)
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background was subtracted by fitting the trace to an exponential decay and the peaks in the resulting trace were fit using 2-5 Gaussians, depending on the trace studied. One Gaussian was always used to fit the amorphous scattering feature from the substrate which has somewhat variable intensity in each scan.
Figure S4. GIWAXS linecuts along the horizontal and vertical axes of the 2D images showing the crystal structure of A) neat PBTIBDT films with 0-5 vol % DIO in-plane and B) neat PBTIBDT films with 0-5 vol% DIO out of plane and C) PBTIBDT:PCBM films with 0-5 vol % DIO in-plane and PBTIBDT:PCBM films with 0-5vol % DIO out of plane.
I q (a
.u.)
2.01.71.41.10.80.50.2
qxy (Å-1)
0% DIO 1% 2% 3% 4% 5%
I q (a
.u.)
2.01.71.41.10.80.50.2
qz (Å-1)
0% DIO 1% 2% 3% 4% 5%
I q (a
.u.)
2.01.71.41.10.80.50.2qxy (Å
-1)
0% DIO 1% 2% 3% 4% 5%
I q (a
.u.)
2.01.71.41.10.80.50.2
qz (Å-1)
0% DIO 3% 1% 4% 2% 5%
A B
C D
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Table S2. GIWAXS d-spacings of PBTIBDT and PCBM domains in neat and blend thin films as a function of vol% DIO.
DIO (vol %)
PBTIBDT lamellar
(neat) (Å) PBTIBDT π-π
(neat) (Å) PBTIBDT lamellar
(blend) (Å) PBTIBDT π-π
(blend) (Å) PCBM
(neat) (Å) PCBM
(blend) (Å) 0 26.2 3.6 25.5 3.6 4.5 4.5 1 27.7 3.6 25.2 3.6 4.5 4.5 2 26.8 3.6 25.5 3.7 4.5 4.5 3 27.6 3.6 27.5 3.7 4.5 4.5 4 27.2 3.6 25.1 3.7 4.6 4.4 5 27.7 3.6 25.3 3.6 4.5 4.5
GISAXS data analysis and linecuts
Figure S5. GISAXS linecuts of PBTIBDT:PCBM blend films with 0-5 vol% DIO describing the domain sizes out of plane.
Inte
nsity
(a.u
.)
4 5 6 7 8 90.1
2
qz (Å-1)
0%DIO 1%DIO 2%DIO 3%DIO 4%DIO 5%DIO
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Spectroelectrochemistry data for PBTIBDT cation signal determination in solutions and films
Figure S6: Spectroelectrochemisty of PBTIBDT solutions in o-dichlorobenzene and neat film showing cation signals at 750-800 nm with a broad feature extending from 1000 nm to longer wavelengths. UV-Vis Absorption spectra for neat PBTIBDT films with 0-5 vol% DIO Figure S7: UV-Vis absorption spectra of neat PBTIBDT films with no DIO and 1-5 vol% DIO. The absorption shows no change in onset absorption and minor shifts in the peak absorption, but an increase in the vibronic structure as DIO concentration is increased, suggesting increased crystallinity of the PBTIBDT regions as DIO concentration is increased.
0.35
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∆OD
(a.u
.)
1000800600400Wavelength (nm)
BTIBDT soln BTIBDT soln w/ FeCl3
BTIBDT film 0V BTIBDT film 1.2V
1.0
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0.6
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Abs
(nor
m)
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0% DIO 1% DIO 2% DIO 3% DIO 4% DIO 5% DIO
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Optical transient absorption within 3 ns delay time window, and fitting parameters for exciton absorption and ground state bleach
Figure S8: Time delays of A) neat PBTIBDT film with 0 vol% DIO and B) PBTIBDT:PCBM blend film with 0 vol% DIO and C) 5 vol% DIO and D) PBTIBDT:PCBM blend film with 3 vol% DIO illustrating the entire visible and near IR spectra. Table S3: Exciton dynamics of PBTIBDT:PCBM blend films
[DIO] (vol %) τ1 (ps) τ2 (ps) τ3 (ps)a τ4 (ps) A1 (%) A2 (%) A3 (%) A4 (%)
0 0.48 (0.01)
4.3 (0.2)
82.8 (10.8)
>3000 57 (3) 15 (2) 22 (1) 6 (0)
1 0.56 (0.03)
5.0 (0.6)
63.8 (11.4)
>3000 64 (4) 8 (3) 22 (2) 6 (0)
2 0.76 (0.04)
4.8 (0.6)
84.3 (20.3)
>3000 59 (6) 11 (4) 22 (2) 8 (1)
3 0.61 (0.03)
5.2 (0.7)
62.6 (17.0)
>3000 61 (5) 10 (4) 21 (2) 8 (1)
4 0.29 (0.01)
3.4 (0.2)
86.7 (9.9)
>3000 70 (3) 12 (1) 13 (1) 4 (0)
5 0.54 (0.02)
4.3 (0.5)
53.6 (10.2)
>3000 64 (4) 10 (3) 20 (2) 6 (0) a Attributed to CAT decay due to overlap of CAT and EX peaks. Error in fit is noted in parentheses.
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(a.u
.)
14001300120011001000900Wavelength (nm)
t0 1ps 2ps 3ps 4ps 10ps 50ps 100ps 500ps 1ns 2ns 3ns
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0.5
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.)
14001300120011001000900Wavelength (nm)
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2.0
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∆OD
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.)
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C
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-4
-2
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140012001000800600400Wavelength (nm)
t0 10 ps 1 ps 50 ps 2 ps 100 ps 3 ps 500 ps 4 ps 3 ns
D
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Table S4: Ground state bleach dynamics of PBTIBDT:PCBM blend films
[DIO] (vol %) τ1 (ps) τ2 (ps) τ3 (ps) τ4 (ps) A1 (%) A2 (%) A3 (%) A4 (%)
0 0.48 (0.01) 4.3 (0.2) 97 (8) >3000 66 (1) 20 (1) 10 (0) 4 (0)
1 0.56 (0.03) 5.0 (0.6) 92 (10) >3000 64 (1) 18 (1) 10 (1) 8 (0)
2 0.76 (0.04) 4.8 (0.6) 70 (10) >3000 67 (2) 21 (2) 6 (1) 6 (0)
3 0.61 (0.03) 5.2 (0.7) 65 (11) >3000 70 (1) 18 (1) 6 (1) 6 (0)
4 0.29 (0.01) 3.4 (0.2) 71 (5) >3000 72 (1) 16 (0) 7 (0) 5 (0)
5 0.54 (0.02) 4.3 (0.5) 50 (8) >3000 76 (1) 16 (1) 4 (1) 4 (0)
Error in fit is noted in parentheses. Table S5: Dynamics of neat PBTIBDT films τ1 (ps) τ2 (ps) τ3 (ps) A1
(%) A2 (%)
A3 (%)
A4 (%)
0 vol%
DIO
CS 0.39 (0.01) NA 60.6 (10.0) 71 (9) NA 26 (2) 3 (1)
EX 0.39 (0.01) 4.3 (0.3) NA 73 (4) 20 (2) NA 7 (0)
GSB 0.39 (0.01) 4.3 (0.3) 60.6 (10.0) 79 (1) 14 (0) 4 (0) 3 (0) 5
vol%
DIO
CS 0.24 (0) NA 68.2 (3.8) 69 (2) NA 23 (1) 7 (0)
EX 0.24 (0) 6.3 (0.4) NA 70 (2) 26 (1) NA 4 (0)
Error in fit is noted in parentheses.
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Nanosecond transient absorption
Figure S9. Decay of cation species at 1070 nm in PBTIBDT:PCBM films as a function of vol % DIO normalized at the highest intensity.
10-5
10-4
10-3
10-2
10-1
100∆O
D (n
orm
)
0.01 0.1 1 10Time (µs)
0%DIO 1%DIO 2%DIO 3%DIO 4%DIO 5%DIO
