Impact of P3HT Materials Properties and Layer Architecture on OPV Device Stability
Rico Meitzner1,2, Tobias Faber3, Shahidul Alam1,2, Aman Amand1,2, Roland Roesch1,2, Mathias Büttner3, Felix Herrmann-Westendorf4, Martin Presselt1,4,18,19, Laura Ciammaruchi5, Iris Visoly-Fisher 5,6, Sjoerd Veenstra7, Amaia Diaz de Zerio8, Xiaofeng Xu8, Ergang Wang8, Christian Müller8, Pavel Troshin9a, 9b, Martin D. Hager 1,2, Sandra Köhn1,2, Michal Dusza10,11, Miron Krassas12, Simon Züfle16,17, E. Kymakis12, Eugene A. Katz5,6, Solenn Berson13, Filip Granek10, Matthieu Manceau13, Francesca Brunetti14,Giuseppina Polino14, Ulrich S. Schubert1,2, Monica Lira-Cantu15, and Harald Hoppe1,2
1 Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller University Jena, Philosophenweg 7a, 07743 Jena, Germany2 Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, Humboldstrasse 10, 07743 Jena, Germany3 Institute of Physics, Technische Universität Ilmenau, Weimarer Straße 32, 98693 Ilmenau,
Germany4 Institute of Physical Chemistry (IPC), Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, Germany5 Department of Sol. Energ. and Environmental Physics, Swiss Inst. for Dryland Environmental and Energy Research, J. Blaustein Institutes for Desert Research, Ben-Gurion University of the Negev, Midreshet Ben-Gurion 8499000, Israel6Ilse Katz Institute for Nanoscale Science and Technology, Ben-Gurion University of the Negev, Beersheva 8410501, Israel7 ECN/Solliance, High Tech Campus 21, 5656 AE Eindhoven, The Netherlands8 Department of Chemistry and Chemical Engineering, Chalmers University of Technology, 41296 Göteborg, Sweden9a Skolkovo Institute of Science and Technology, Nobel st. 3, Moscow, 121205, Russia
9b IPCP RAS, Semenov Prospect 1, Chernogolovka, 141432, Russia.10 Wroclaw Research Centre EIT+, Stablowicka 147, 54-066 Wroclaw, Poland11 Institute of Low Temperature and Structure Research, Polish Academy of Science, Okolna 2, 50-422 Wroclaw, Poland12 Center of Materials Technology and Photonics, Electrical Engineering Department, School
of Applied Technology, Technological Educational Institute (TEI) of Crete, Heraklion, 71004 Crete, Greece
1
13 CEA, LITEN/DTS, Laboratoire des technologies pour les Modules Photovoltaïques, Savoie Technolac, BP 332, 50 Avenue du Lac Léman, 73377 Le Bourget-du-Lac, France14 CHOSE (Centre for Hybrid and Organic Sol. Energ.), Department of Electronic Engineering, University of Rome Tor Vergata, Via del Politecnico 1, 00133, Rome, Italy15 Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and the Barcelona Institute of Science and Technology (BIST). Building ICN2, Campus UAB E-08193, Bellaterra, Barcelona, Spain.16
Institute of Computational Physics, Zurich University of Applied Sciences (ZHAW), Wildbachstrasse 21, 8400 Winterthur17
Fluxim AG, Katharina-Sulzer-Platz 2, 8400 Winterthur, Switzerland 18 Leibniz Institute of Photonic Technology (IPHT), Albert-Einstein-Str. 9, 07745 Jena, Germany19 sciclus GmbH & Co. KG, Moritz-von-Rohr-Str. 1a, 07745 Jena, Germany
Content2
1 Solution storage and processing conditions of the different P3HT solutions......................5
2 Processing of transport layers:...........................................................................................12
2.1 CEA............................................................................................................................12
2.2 EIT+...........................................................................................................................12
2.3 ICN2...........................................................................................................................13
2.4 TEIC...........................................................................................................................13
2.5 UTV............................................................................................................................13
3 Estimated and Calculated Thicknesses for EIT+ solar cells..............................................13
4 Initial Efficiencies of Solar Cells by Producer and for each Experiement........................14
5 Spectrum of lamp used in aging setup for ISOS-L2 degradation......................................15
6 Spectrum and site at Sde Boker in Israel where ISOS-O1 measurements were performed15
7 Ageing setup used for ISOS-D2 at Solliance, Einhoven...................................................17
8 Normalization of the Starting Short Circuit Current Density of the Solar Cells Aged Under ISOS-L2.........................................................................................................................17
9 TGA measurements of the different P3HT batches...........................................................18
10 SEC measurements of the different P3HT batches........................................................18
11 DSC measurements of the different P3HT batches.......................................................20
12 NMR measurement results of the different P3HT batches used to determine regio-regularity...................................................................................................................................21
13 Photovoltaic parameter development of the solar cells used in the ISOS-L2 experiments...............................................................................................................................26
14 Photovoltaic parameter development during ISOS-D2 experiments.............................34
15 Photovoltaic parameter development during ISOS-O1 experiments.............................43
16 EQE spectra before and after ISOS-L2 aging................................................................51
17 LEY fits of the solar cells aged under ISOS-L2 conditions – Determination of ageing parameters (T80, TS, TS,80, LEY, E80, ES and ES,80) from fits to the PCE decay under ISOS-L2 conditions..................................................................................................................................53
18 Bibliography..................................................................................................................61
1 Solution storage and processing conditions of the different P3HT solutions
In the following the solutions as well as their recommended processing parameters are summarized:
3
P3HT-I solution was prepared in CB with a concentration of 15 mg/mL P3HT and a 1:0.88 ratio between P3HT:PCBM (PCBM: >99.5% purity). The recommended pre-processing temperature was set to 60°C while stirring at 500 rpm, and the processing temperature was RT with no stirring. For deposition a spin frequency of 100 rpm for 3s followed by 1500 rpm for 40s was recommended by the provider.
P3HT-II solution was prepared in dichlorobenzene with a concentration of 30 mg/mL P3HT and a weight ratio of 3:2 P3HT:PCBM (PCBM purity was >99%). Pre-processing temperature was recommended as 60°C while stirring at 500 rpm. Processing of the active layers was performed at 40°C under no stirring. For deposition a spin frequency of 800 rpm for 100 s was recommended by the provider.
P3HT-III solution was prepared in CB with a concentration of 18 mg P3HT per mL and a weight ratio of 3:2 for P3HT:PCBM (PCBM purity was >99%). Storage was recommended at room temperature and 500 rpm stirring, pre-processing at 50°C and processing conditions were given at 50°C. For deposition a spin frequency of 800 rpm for 60 s was recommended by the provider.
P3HT-IV solution was prepared in m-xylene with a concentration of 15 mg/mL P3HT and a weight ratio of 2:1 (PCBM purity of >99%). Storage was recommended at 50°C while stirring at 700 rpm. Processing was performed at room temperature without stirring. For deposition a spin frequency of 600 rpm for 60 s was recommended by the provider.
P3HT-V solution was prepared in CB with a P3HT concentration of 15 mg/mL and a weight ratio of 3:2 (P3HT:PCBM). It had a recommended pre-processing and processing temperatures of 50°C and recommended stirring of 500 rpm during storage. For deposition a spin frequency of 500 rpm for 120s followed by 1500 rpm for 5s was recommended by the provider.
Different labs deviated slightly from these conditions; for further details, please see tables S1-S5 in the supplementary information.
Table 1: Production conditions of CEA solar cells
P3HT:PC60BM
Solution
Pre-processing
Processing condition
Deposition Drying Condition
Annealing Condition
4
condition
P3HT-I Solution at 60°C one day
before
Kept stirring for one night
Temperature reduced one hour before
coating to RT
Kept stirring
hour before solution at ambient
temperature
under stirring
glove box
1st step: 100 rpm, 3
s
2nd step: 1500 rpm,
40 s
After spin coating: substrate
drying few s on spin coating chuck
Substrate dried on hot plate 50°C
5 min
Before deposition of the top electrode,
120°C
10 min
P3HT-II 60°C under stirring for 4
hours
40°C under stirring
overnight
Heating to 40°C no stirring
glove box
800 rpm, 100 s
Drying on the spin coater
(during the 100 s of spinning)
Annealing before
electrode evaporation
30 min 130oC
P3HT-III Heating to 50°C under
stirring
Permanent stirring at 500 rpm
Processing temperature
50°C
800 rpm - Post-Production annealing
180°C
10 min
P3HT-IV Heating to 60°C under
stirring for 10 min minimum
cool to 50°C (at 600 rpm)
Permanent stirring at 600 rpm
Processing temperature
50°C
600 rpm, 60 sec
- Post-Production annealing
160°C
5 min (inert gas)
P3HT-V Heating to 50°C under
stirring overnight
- 1st step: 500 rpm, 120 sec
2nd step: 1500 rpm, 5
sec
- Post deposition annealing
120oC,
20 min (inert gas)
Table 2: Production conditions of EIT+ solar cells
5
P3HT:PC60BM
Solution
Pre-processin
g Condition
Processing
Condition
Deposition
Drying conditio
n
Annealing
Condition
P3HT-I 40°C under stirring
overnight
Heating to 40°C
no stirring
100 rpm, 3 s
1500 rpm, 40 s
Drying on spin coater
(during spinning)
5 min, 50°C
20 min, 130°C
P3HT-II 60°C under stirring
4 hours
40°C under stirring
overnight
Heating to 40°C
no stirring
800 rpm, 100 s
Drying on spin coater
(during spinning)
30 min, 130°C
P3HT-II (50°C)
40°C under stirring
overnight
Heating to 40°C
no stirring
Drop casting, 50
µl
Drying 100 s on
spin chuck
15 min, 50°C
P3HT-III (50°C)
40°C under stirring
overnight
Heating to 40°C
no stirring
600 rpm, 100 s
Drying on the spin
coater (during
spinning)
15 min, 160°C
P3HT-IV (50°C)
40°C under stirring
overnight
Heating to 40°C
no stirring
600 rpm, 100 s
Drying on the spin
coater (during
spinning)
20 min, 130°C
P3HT-V 40°C under stirring
overnight
Heating to 40°C
no stirring
500 rpm, 100 s
1500 rpm, 5 s
Drying on the spin
coater (during
spinning)
20 min, 130°C
Table 3: Production conditions of ICN2 solar cells
6
P3HT:PC60BM
Solution
Pre-Processing Condition
Processing Condition
Deposition Drying Condition
Annealing Condition
P3HT-I 60°C under stirring
during night
hour before:
the solution left at
ambient temperature
under stirring
glove box
1st step: 100 rpm, 3 s
2nd step: 1500 rpm, 40
s
After spin coating:
substrate drying few s
on spin coating chuck
substrate drying on hot plate 50°C, 5
min
Pre-annealing:
5 min, 50°C
Annealing:
10 min, 120°C
P3HT-II 60°C
stirring for 4 hours
40°C
stirring overnight
Heating to 40°C
no stirring
800 rpm, 100 s
Drying on the spin coater
(during the 100 s of spinning)
Annealing before
electrode evaporation
30 min130°C
P3HT-III 50°C under stirring
Stirring at 500 rpm
Processing temperature
50°C
800 rpm - Post-Production annealing
10 min, 180°C
P3HT-IV 60°C under stirring for
10 min
cool to 50°C
Stirring at 500 rpm
Processing temperature
50oC
600 rpm, 60 sec
- Post-Production annealing
5 min, 160°C (inert gas)
P3HT-V Heating to 50°C
stirring overnight
- 1st step: 500 rpm, 120 s
2nd step: 1500 rpm, 5
s
- Post deposition annealing:
120°C, 20 min (inert
gas)
Table 4: Production conditions of TEIC solar cells
7
P3HT:PC60BM
Solution
Pre-processing Condition
Processing Condition
Deposition Drying Condition
Annealing Condition
P3HT-I Heating to 70°C
Overnight stirring
Substrate and
Solution at RT
100 rpm, 3 s
1500 rpm, 40 s in
glove box
During spin coating
Pre-annealing
5 min, 50°C
10 min, 120°C
P3HT-II Heating to 70°C
Overnight stirring
Substrate and
Solution at RT
1000 rpm, 110 s in
glove box
During spin coating
Annealing after
electrodes
30 min 130°C
P3HT-III Heating to 70°C
Overnight stirring
Substrate and
Solution at RT
1000 rpm, 110 s in
glove box
During spin coating
Pre-annealing
15 min, 160°C
P3HT-IV Heating to 70°C
Overnight stirring
Substrate and
Solution at RT
1000 rpm, 110 s in
glove box
During spin coating
Annealing after
electrodes
5 min, 160°C
P3HT-V Heating to 70°C
Overnight stirring
Substrate and
Solution at RT
500 rpm, 120 s
1500 rpm, 5 s in
glove box
During spin coating
Annealing after
electrodes
15 min, 160°C
Table 5: Production conditions of UTV solar cells
8
P3HT:PC60BM
Solution
Pre-Processing Condition
Processing Condition
Deposition Drying Condition
Annealing Condition
P3HT-I Heating to 60°C
stirring overnight
hour before: solution left
at RT
under stirring
glove box
1st step: 100 rpm, 3 s
2nd step: 1500 rpm, 40
s
After spin coating:
substrate drying few s
on spin coating chuck
substrate drying on hot plate 50°C, 5
min
Pre-annealing:
5 min, 50°C
Annealing:
10 min, 120°C
P3HT-II 60°C under stirring for 4 hours, 40°C
under stirring
overnight
Cooling to 40°C no stirring
800 rpm, 100 s
Drying on the spin coater
(during the 100 s of spinning)
Annealing before
electrode evaporation
30 min 130°C
P3HT-III 50°C under stirring
Permanent stirring at 500 rpm
Processing temperature
50oC
800 rpm - Post-Production annealing
10 min, 180°C
P3HT-IV 60oC
stirring overnight
10 min cooling to
50°C
Permanent stirring at 600 rpm
Processing temperature
50°C
600 rpm, 60 s
- Post-Production annealing
5 min, 160°C (inert gas)
P3HT-V Heating to 50°C
stirring overnight
- 500 rpm, 120 s
1500 rpm, 5 sec
- Post deposition annealing
120°C, 20 min (inert
gas)
9
2 Processing of transport layers:2.1 CEAThe ETL layer was obtained from zinc oxide nanoparticle dispersion in ethanol (40% in weight). The supplier guarantees a particle size below 130 nm, and a diffusion light scattering measurement confirmed an average size close to 40 nm. For the ETL, a 50-100 nm thick ZnO film was then deposited by spincoating and baked for 5 min at 140 °C. The active layers were deposited according to the procedure described in Table 1. PEDOT:PSS solution was spin-coated onto the active layer to form the HTL layer 50-100 nm afterwards annealing at 120°C for 5 minutes was performed. A HTL reference layer was cast from a conductive PEDOT:PSS dispersion in aqueous solvent (Clevios P Form). A silver electrode (thickness 100 nm) was evaporated through a shadow mask to complete the devices.
2.2 EIT+Cleaning was performed on pre-patterned ITO substrates on glass in acetone and isopropanol for 30 minutes each in an ultrasonic bath. A zinc oxide nanoparticle dispersion in ethanol (Sigma Aldrich) was deposited by spin coating at 7000 rpm and annealed at 500°C in air [1] reaching a thickness of 50 nm. Than the different active layers were deposited according to the procedures listed in Error: Reference source not found. Finally the molybdenum oxide (~12 nm) and silver (~120 nm) were thermally evaporated at a pressure of 2 ×10−6 mbar .
2.3 ICN2The V2O5 solution was done according to an earlier published procedure [2]. FTO on glass substrates were acquired from SOLEMS these were cleaned in a water-soap solution, rinsed with deionized water. Following the substrates were ultrasonicated in ethanol (99%), dried in a N2 flux and ozone treated in a UV-surface decontamination system (Novascan, PSD-UV). A dense ZnO buffer layer from sol–gel solution was prepared by spin coating at 1500 rpm [3]. The ZnO sol–gel was prepared as follows: 2.0g of zinc acetate and 1.07g of diethanol amine (DEA) were dissolved in 10 mL of isopropanol and heated at 60 ºC for about 10 min until total dissolution, then the solution was diluted with ethanol (1 : 1) and filtered through a 0.45 mm pore membrane (Albet). ZnO was deposited by spin coating with a spin frequency of 1000 rpm. The substrates were sintered at 450 ºC for 2 h to form a dense ZnO layer of about 80 nm. Following the different active layers were deposited according the procedures given in Error: Reference source not found. Afterwards the V2O5 layer was deposited by spin coating at 1000 rpm according to the procedure described by Teron-Escobar et al [2]. And finally silver (100 nm) was thermally evaporated at a pressure of 10-7 Torr and a rate of 1 Å/s [2].
2.4 TEICAs substrates ITO on glass was used with a sheet resistance of 20 Ohm/sq, cleaning was performed in a 3-step process. PEDOT:PSS from an aqueous solution was spin cast at 6000 rpm for 60 seconds. Afterwards the samples were thermally annealed at 120°C for 15 minutes in an oven, resulting in a layer thickness of around 30 nm. The active layers was deposited according to the details given in Table 4. Afterwards Calcium was thermally evaporated at a pressure of 10-6 mbars with a rate of 0.4 Å/s until a thickness of 5 nm was reached. Afterwards Aluminium was also thermally evaporated at a similar pressure until a final Al layer thickness of 100 nm was reached [4].
10
2.5 UTVFTO-coated glass substrates (Kintec 15Ω/) were used as substrates for the manufacture of the solar cells. As an ETL, PEIE (Polyethylenimine ethoxylated) solution of 35–40 wt % PEIE in water, as received from Aldrich, was diluted with 2-methoxyethanol to a concentration of 0.4 wt-%, following this PEIE solution was spin-coated at 5000 rpm for 60 s and afterwards dried at 120°C for 10 minutes on a hotplate in ambient air thereby a thickness of 10 nm was achieved. Following the active layers were deposited according to the procedures given in Table 5. A MoO3 (5 nm) was deposited by thermal evaporation followed by a Ag (100 nm) layer which was also thermally evaporated at a pressure of 10-6 mbar. Devices were sealed using Parafilm and a squared glass lid by heating the sample to 90°C and pressing the glass lid with 0.9 bar pressure against the solar cell [5].
3 Estimated and Calculated Thicknesses for EIT+ solar cellsTable 6: Thicknesses estimated from comparison of measured EQE spectra with optical simulations of EQE spectra for P3HT:PCBM solar cells and calculated from capacitance measurements.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-VThickness (nm) EIT+ from Capacitance
326 137 68 62 98
Thickness (nm) EIT+ from EQE
190 70-80 70-80 110 70-80
Figure 1: EQE spectra from optical simulations for P3HT:PCBM.
11
4 Initial Efficiencies of Solar Cells by Producer and for each Experiement
Table 7: Starting efficiencies of the different cell manufacturers.
Manufacturer-Material
ISOS-L1 ISOS-O1 ISOS-D2
CEA: P3HT-I 2.4% 1.21% 2.54%
CEA: P3HT-II 0.34% 0.58% 0.14%
CEA: P3HT-IV 1.35% 0.81%
CEA: P3HT-V 2.58% 1.37% 0.04%
EIT+: P3HT-I 2.04% 2.35% 2.24%
EIT+: P3HT-II 1.98% 2.3% 2.36%
EIT+: P3HT-III 0.92% 0.77% 0.8%
EIT+: P3HT-IV 0.88% 1% 1.11%
EIT+: P3HT-V 0.88% 0.81% 0.73%
ICN2: P3HT-I 0.07% 1.71% 1.2%
ICN2: P3HT-II 0.46% 0.97% 1.31%
ICN2: P3HT-III 0.04% 0.31%
ICN2: P3HT-IV 0.51%
ICN2: P3HT-V 1.1% 0.81%
TEIC: P3HT-I 1.95% 1.55%
TEIC: P3HT-II 1.88% 1.54% 2.38%
TEIC: P3HT-III 2.95% 2.82%
TEIC: P3HT-IV 2.17% 2.43% 1.95%
TEIC: P3HT-V 2.55% 2.18% 2.26%
UTV: P3HT-I 2.57% 3.05% 1.6%
UTV: P3HT-II 2.33% 1.69% 1.87%
UTV: P3HT-III 3.2% 2.9% 2.84%
UTV: P3HT-IV 3.25% 3.11% 0.13%
UTV: P3HT-V 3.98% 4% 3.66%
12
5 Spectrum of lamp used in aging setup for ISOS-L2 degradation
Figure 2: Full view of L2 light source spectrum in comparison to AM1.5G spectrum.
6 Spectrum and site at Sde Boker in Israel where ISOS-O1 measurements were performed
Figure 3: Solar spectrum in Sde Boker at around the time of aging of the solar cells. As can be seen it is very close to the standard AM1.5G spectrum.
13
Figure 4: For outdoor aging (close to O1) samples were mounted over day under the sun, while IV-characterization took place under a solar simulator indoors.
7 Ageing setup used for ISOS-D2 at Solliance, Einhoven
Figure 5: Sample arrangement for investigation of D2 aging.
8 Normalization of the Starting Short Circuit Current Density of the Solar Cells Aged Under ISOS-L2
The initial value of the short circuit current density of those solar cells aged under ISOS-L2 conditions was corrected for proper analysis to the value obtained by EQE measurements before ageing. Based on this correction, all values during ageing were adapted and similarly the PCE.
14
9 TGA measurements of the different P3HT batches
Figure 6: TGA Measurements of the P3HT batches.
15
10 SEC measurements of the different P3HT batches
Figure 7: SEC measurement results of the P3HT batches. (Trichlorobenzene as solvent and polystyrene as calibration standard)
Table 8: Polymer properties of the P3HT batches determined by GPC, TGA and DSC at Chalmers University.
Polymer Mn
(kg/mol)Mw
(kg/mol)ᴆ (-) [PDI]
RR (%) TD
(°C)TM
(°C)TC
(°C)ΔHM
(J/g)
P3HT-I 30 59 2.0 96 455 237 201 18
P3HT-II 24 54 2.3 94 455 227 184 17
P3HT-III 11 22 2.0 96 455 227 197 20
P3HT-IV 26 71 2.7 90 456 222 189 14
P3HT-V 25 60 2.4 95 455 236 198 21
16
11 DSC measurements of the different P3HT batches
Figure 8: Measurements of the P3HT batches.
17
12 NMR measurement results of the different P3HT batches used to determine regio-regularity
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
-5000
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
55000
60000
65000
70000
0.04
1.00
0.05
80.
885
0.89
00.
903
0.91
40.
920
1.32
51.
334
1.34
31.
350
1.36
11.
394
1.41
01.
428
1.44
71.
541
1.67
71.
695
1.71
2
2.58
22.
602
2.72
42.
773
2.79
32.
812
6.88
86.
940
6.95
16.
968
6.98
16.
984
7.24
27.
245
7.25
07.
251
7.25
2
102030405060708090100110120130140150f1 (ppm)
0
10
20
30
40
50
60
70
80
90
100
110
12014.0
94
22.6
27
29.2
3529
.442
30.4
8231
.670
76.6
5576
.972
77.2
90
128.
568
130.
453
133.
666
139.
856
Figure 9: NMR measurement results of P3HT-I. (Done in chloroform-d (CDCl3); top: 1H NMR Spectrum, bottom: 13C NMR spectrum.
18
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
100000
0.06
1.00
0.05
80.
059
0.88
50.
902
0.92
01.
325
1.33
31.
343
1.35
01.
360
1.39
41.
410
1.42
81.
446
1.65
81.
677
1.69
51.
712
2.77
32.
792
2.81
2
6.96
86.
981
7.24
37.
245
7.24
67.
248
7.24
97.
250
0102030405060708090100110120130140150f1 (ppm)
-10
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
14.0
96
22.6
30
29.2
3729
.444
30.4
8531
.672
76.6
5876
.975
77.2
93
128.
569
130.
454
133.
667
139.
856
Figure 10: NMR measurement results of P3HT-II. (Done in chloroform-d (CDCl3); top: 1H NMR Spectrum, bottom: 13C NMR spectrum.
.
19
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
100000
110000
0.06
1.00
0.05
7
0.85
10.
884
0.88
90.
902
0.91
30.
919
1.31
61.
324
1.33
21.
342
1.34
91.
360
1.40
91.
427
1.44
61.
535
1.67
61.
694
1.71
3
2.77
22.
792
2.81
1
6.92
66.
950
6.95
86.
967
7.24
6
0102030405060708090100110120130140150f1 (ppm)
-20
-10
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
14.0
99
22.6
32
29.2
4129
.447
30.4
8731
.676
76.6
6176
.978
77.2
96
128.
568
130.
456
133.
671
139.
858
Figure 11: NMR measurement results of P3HT-III. (Done in chloroform-d (CDCl3); top: 1H NMR Spectrum, bottom: 13C NMR spectrum.
20
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
55000
0.10
1.00
0.05
80.
847
0.86
40.
871
0.88
40.
888
0.90
20.
914
0.92
01.
324
1.33
31.
343
1.35
01.
360
1.41
01.
427
1.44
51.
535
1.67
61.
695
1.71
1
2.77
32.
792
2.81
1
6.95
16.
958
6.96
76.
982
6.98
46.
990
7.01
37.
019
7.03
77.
246
0102030405060708090100110120130140150f1 (ppm)
-20
-10
0
10
20
30
40
50
60
70
80
90
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250
14.1
02
22.6
35
29.2
4329
.449
30.4
8931
.678
76.6
6376
.980
77.2
98
128.
569
130.
459
133.
672
139.
858
Figure 12: NMR measurement results of P3HT-IV. (Done in chloroform-d (CDCl3); top: 1H NMR Spectrum, bottom: 13C NMR spectrum.
21
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
0.05
1.00
0.05
9
0.88
50.
891
0.90
30.
915
0.92
10.
948
1.31
71.
325
1.33
41.
344
1.35
11.
361
1.41
11.
429
1.44
81.
535
1.67
81.
696
2.77
42.
794
2.81
3
6.92
76.
940
6.95
16.
969
6.98
16.
991
7.24
27.
243
7.24
67.
248
0102030405060708090100110120130140f1 (ppm)
-20
0
20
40
60
80
100
120
140
160
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28014.1
00
22.6
34
29.2
4229
.449
30.4
8831
.677
76.6
6176
.979
77.2
97
128.
570
130.
457
133.
672
139.
859
Figure 13: NMR measurement results of P3HT-V. (Done in chloroform-d (CDCl3); top: 1H NMR Spectrum, bottom: 13C NMR spectrum.
22
13 Photovoltaic parameter development of the solar cells used in the ISOS-L2 experiments
Figure 14: L2 Open circuit voltage of CEA solar cells.
Figure 15: L2 Short circuit current density of CEA solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
23
Figure 16: L2 Fill factor of CEA solar cells.
Figure 17: L2 Open circuit voltage of EIT+ solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
24
Figure 18: L2 Short circuit current density of EIT+ solar cells.
Figure 19: L2 Fill factor of EIT+ solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
25
Figure 20: L2 Open circuit voltage of ICN2 solar cells.
Figure 21: L2 Short circuit current density of ICN2 solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
26
Figure 22: L2 Fill factor of ICN2 solar cells.
Figure 23: L2 Open Ciruit Voltage of TEIC solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
27
Figure 24: L2 Short circuit current density of TEIC solar cells.
Figure 25: L2 Fill factor of TEIC solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
28
Figure 26: L2 Open circuit voltage of UTV solar cells.
Figure 27: L2 Short circuit current density of UTV solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
29
Figure 28: L2 Fill factor of UTV solar cells.
30
14 Photovoltaic parameter development during ISOS-D2 experiments
Figure 29: D2 open circuit voltage of CEA solar cells.
Figure 30: D2 short circuit current density of CEA solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
31
Figure 29: D2 fill factor of CEA solar cells.
Figure 30: D2 open circuit voltage of EIT+ solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
32
Figure 31: D2 short circuit current density of EIT+ solar cells.
Figure 31: D2 fill factor of EIT+ solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
33
Figure 33: D2 open circuit voltage of ICN2 solar cells.
Figure 34: D2 short circuit current density of ICN2 solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
34
Figure 32: D2 fill factor of ICN2 solar cells.
Figure 33: D2 open circuit voltage of TEIC solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
35
Figure 34: D2 short circuit current density of TEIC solar cells.
Figure 35: D2 fill factor of TEIC solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
36
Figure 36: D2 open circuit voltage of UTV solar cells.
Figure 40: D2 short circuit current density of UTV solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
37
Figure 41: D2 fill factor of UTV solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
38
15 Photovoltaic parameter development during ISOS-O1 experiments
Figure 42: O1 Relative Open circuit voltage of CEA solar cells.
Figure 43: O1 Relative Short circuit current density of CEA solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
39
Figure 44: O1 relative fill factor of CEA solar cells.
Figure 45: O1 relative open circuit voltage of EIT+ solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
40
Figure 46: O1 relative short circuit current density of EIT+ solar cells.
Figure 47: O1 relative fill factor of EIT+ solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
41
Figure 48: O1 relative open circuit voltage of ICN2 solar cells.
Figure 49: O1 relative short circuit current density of ICN2 solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
42
Figure 50: O1 relative fill factor of ICN2 solar cells.
Figure 51: O1 relative open circuit voltage of TEIC solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
43
Figure 37: O1 relative short circuit current density of ICN2 solar cells.
Figure 38: O1 relative fill factor of TEIC solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
44
Figure 39: O1 relative open circuit voltage of UTV solar cells.
Figure 40: O1 relative short circuit current density of UTV solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
45
Figure 41: O1 relative fill factor of UTV solar cells.
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
46
16 EQE spectra before and after ISOS-L2 aging
Figure 42: EQE spectra before (left) and after (right) aging for L2
47
300 400 500 600 700 800 9000
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80
CEAE
QE
(%)
Wavelength (nm)
300 400 500 600 700 800 9000
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ICN2
Wavelength (nm)
300 400 500 600 700 800 9000
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EIT+
Wavelength (nm)
300 400 500 600 700 800 9000
10
20
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CEA
EQ
E (%
)
Wavelength (nm)
300 400 500 600 700 800 9000
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80
ICN2
Wavelength (nm)
300 400 500 600 700 800 9000
10
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50
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80
EIT+
Wavelength (nm)
Figure 43: EQE spectra before (left) and after (right) aging for L2
P3HT-I P3HT-II P3HT-III P3HT-IV P3HT-V
48
300 400 500 600 700 800 9000
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80
TEIC
EQ
E (%
)
Wavelength (nm)
300 400 500 600 700 800 9000
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UTV
EQ
E (%
)
Wavelength (nm)
300 400 500 600 700 800 9000
10
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TEICE
QE
(%)
Wavelength (nm)
17 LEY fits of the solar cells aged under ISOS-L2 conditions – Determination of ageing parameters (T80, TS, TS,80, LEY, E80, ES
and ES,80) from fits to the PCE decay under ISOS-L2 conditions
Figure 44: Fit for CEA P3HT-I from L2 experiment.
Figure 60: Fit for CEA P3HT-II from L2 experiment.
49
Figure 61: Fit for CEA P3HT-IV from L2 experiment.
Figure 62: Fit for CEA P3HT-V from L2 experiment.
50
Figure 63: Fit for EIT+ P3HT-I from L2 experiment.
Figure 45: Fit for EIT+ P3HT-II from L2 experiment.
51
Figure 46: Fit for EIT+ P3HT-III from L2 experiment.
Figure 47: Fit for EIT+ P3HT-IV from L2 experiment.
Figure 48: Fit for EIT+ P3HT-V from L2 experiment.
52
Figure 49: Fit for ICN2 P3HT-I from L2 experiment.
Figure 50: Fit for ICN2 P3HT-II from L2 experiment.
Figure 70: Fit for ICN2 P3HT-IV from L2 experiment.
53
Figure 71: Fit for ICN2 P3HT-V from L2 experiment.
Figure 51: Fit for TEIC P3HT-I from L2 experiment.
Figure 52: Fit for TEIC P3HT-II from L2 experiment.
54
Figure 53: Fit for TEIC P3HT-III from L2 experiment.
Figure 54: Fit for TEIC P3HT-IV from L2 experiment.
Figure 55: Fit for TEIC P3HT-V from L2 experiment.
55
Figure 56: Fit for UTV P3HT-I from L2 experiment.
Figure 57: Fit for UTV P3HT-III from L2 experiment.
Figure 58: Fit for UTV P3HT-IV from L2 experiment.
56
Figure 80: Fit for UTV P3HT-V from L2 experiment.
18 Bibliography
[1] M. Dusza, W. Strek, F. Granek, Significance of light-soaking effect in proper analysis of degradation dynamics of organic solar cells, SPIE, 2016.[2] G. Terán-Escobar, J. Pampel, J.M. Caicedo, M. Lira-Cantú, Low-temperature, solution-processed, layered V2O5 hydrate as the hole-transport layer for stable organic solar cells, Energy & Environmental Science, 6 (2013) 3088-3098.[3] I. Gonzalez-Valls, M. Lira-Cantu, Dye sensitized solar cells based on vertically-aligned ZnO nanorods: effect of UV light on power conversion efficiency and lifetime, Energy & Environmental Science, 3 (2010) 789-795.[4] M. Krassas, G. Kakavelakis, M.M. Stylianakis, N. Vaenas, E. Stratakis, E. Kymakis, Efficiency enhancement of organic photovoltaic devices by embedding uncapped Al nanoparticles in the hole transport layer, RSC Advances, 5 (2015) 71704-71708.[5] G. Polino, S. Casaluci, M. Dianetti, S. Dell'Elce, A. Liscio, V. Mirruzzo, G. Cardone, G. Susanna, L. Salamandra, T.M. Brown, A. Reale, A. Di Carlo, F. Brunetti, Inverted Bulk-Heterojunction Solar Cells using Polyethylenimine-Ethoxylated Processed from a Fully Aqueous Dispersion as Electron-Transport Layer, Energy Technology, 3 (2015) 1152-1158.
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