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

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14.1

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29.2

4329

.449

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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

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9

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891

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915

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948

1.31

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325

1.33

41.

344

1.35

11.

361

1.41

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429

1.44

81.

535

1.67

81.

696

2.77

42.

794

2.81

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6.92

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940

6.95

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969

6.98

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991

7.24

27.

243

7.24

67.

248

0102030405060708090100110120130140f1 (ppm)

-20

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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

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CEAE

QE

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EIT+

Wavelength (nm)

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E (%

)

Wavelength (nm)

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ICN2

Wavelength (nm)

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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

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QE

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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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