Dye-sensitized and perovskite solar cells

Image:- NASA

1. Introduction2. Device architecture and operation3. Manufacturing issues4. Summary

Dye-sensitized and perovskite solar cellsSupersolar Research Methods Workshop Liverpool University, 5th April 2016

Peter HollimanSchool of Chemistry, Bangor Universityp.j.holliman@bangor.ac.uk

1. Introduction

PV landscapeTechnology choice

92 elements

Crust - 2 x 1022 kg

Atmosphere - 5 x 1018 kg

Emissions

An estimated 4,267 deaths (2008)Up to 9% of deaths due to airborne pollution (2012)

London

More solar energy falls on the Earths surface every day than the whole of humankind could consume in 27 years.

Solar farms

Wrexham 13.1MW, 62 acres

Deeside 45MW, 220 acres

Caernarfon 15MW, 75 acres

Anglesey 49MW, 180 acres

122MW

547 acres

417 football pitches

Geography

Source:- National Renewable Energy Laboratory (US)

2. Device architecture and operation

2. Device operation & architecture

Dye-sensitized solar cellsPerovskites

Electron passes viaelectrolyte to dye

Inter (semiconductor) particle electron transfer to electrode

Electron passes around the circuit

Dye absorbs light and electron jumps to create an excited

state

Semiconductor

Dye

CounterElectrode

WorkingElectrode

DSC operation

I3-/ I-

TiO2

Ef

Reverseillumination

e-

TiO2 on Working

Electrode

Dye

Pt on Counter

Electrode

Forwardillumination

Electricity

Electrolyte

Voc

Substrate cleaning(20 min)

TiO2printing(5 min)

Sinter @ 450C(30 min)

Drying(5 min)

TiCl4treatment(30 min)

Dyeing(24 hours)

Re-sinter@ 450C(30 min)

Working Electrode

Counter Electrode

Substrate cleaning(20 min)

H2PtCl6deposition

(5 min)

Drying(5 min)

Sinter@400C(30 min)

DSC manufacturing

TiO2 Working Electrode

I3-/ I-

TiO2

Ef

e-

TiO2 on Working

Electrode

Dye

Pt on Counter

Electrode

Electrolyte

Sintering

TiO2Printing

pasteBinder + solvent

Printing Mesoporous Film

Reaction front moves from outside inwards

Radiant Heat

Shrinkage, necking, surface versus core

Bulk

SurfaceNecking

5 m = 250 particles

Meso-porous photo-electrodes

Solventevaporation

CO2 + H2O

Pre-made TiO2Binder (polymer)Solvent

PrintingRelaxationSolvent loss

CombustionEnergy balanceOxygen demand

Sintering global processes

Crack free, film thickness, substrate roughness, particle surfaces, mechanical strength

Why a binder?Printed

Sintered

The blancmange effect!

TiO2SolventBinder

Low T sintering peroxide combustion additives

Holliman et al., J. Mater. Chem. A, 2014, 2, 11134.

CO2 + H2OO2

ZnO2 ZnO + O2

P25

P25/CaO2

P25/ZnO2

P25/MgO2

5% 10% 15%

Absorber

I3-/ I-

TiO2

Ef

e-

TiO2 on Working

Electrode

Dye

Pt on Counter

Electrode

Electrolyte

Dye absorbers for light harvesting

0.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75

300 400 500 600 700 800 900 1000 1100 1200 1300

( )

Wavelength (nm)

Light harvesting

Record DSC (14.3%)

Silyl linkerADEKA-1

TriarylamineLEG-4N

S

S S

S

NH

CN

O

C6H13

C6H13

C6H13

C6H13

SiOMe

MeO

OMe

N

OOC4H9S

C4H9

O

O C4H9

C4H9

S

C6H13C6H13 CN

COOH

Yano et al., Chem. Commun., 2015, 51, 18894.

Jsc = 18.27 mAcm-2Voc = 1.01 VFF = 0.77

Co redox couple

NN

N

N

NN

Co

2+ / 3+

SealTiO2 film

Hole

FTO glass Electrolyte

SealDye solution

Outflow for dye solution

Valve

Syringe

Ultra-fast co-sensitization

P.J. Holliman, M.L. Davies, A. Connell, B. Vaca Velasco and T.M. Watson, Chem. Comm., 2010, 46, 7256-7258

Dye time lapse (60x)

Ultra-fast co-sensitization

Ru

N

C

S

NC

S

COOH

COOH(n

-Bu)4NOOC

COON(n-Bu)4

SQ1 ( = 3.7%) N719 ( = 6.0%) N719 +SQ1 ( = 8.0%)

-O

O-

N

N

O

OH

P.J. Holliman, M.L. Davies, A. Connell, B. Vaca Velasco and T.M. Watson, Chem. Comm., 2010, 46, 7256-7258

400 600 8000

10

20

30

40

50

60

70

80

after partial remova SQ1 added

QE

WL/nm

EQE

Co-sensitization

= 5.0%

= 6.1%

= 3.4%SQ2

C8H17

COOH

C2H5

N

N+

O

O-

NOH

O O

C12H25

Connell and Holliman et al., J. Mater. Chem. A, 2014, 2(11), 4055 - 4066.

Chart1

-41.76-26.69

-24.15-5.648

-6.0915.309

5.45211.5

11.116

16.3416.82

23.9214.39

36.3514.79

49.7324.2

60.736.91

67.4647.62

72.4854.76

75.0860.78

75.7665.36

75.7168.51

75.4570.28

75.1771.1

74.8871.79

75.1372.03

75.6971.21

75.868.38

75.3563.11

74.3155.5

71.6946.9

65.9539.04

56.5433.25

44.5629.93

32.3729.14

21.7330.57

13.5834.11

7.97739.63

4.60445.9

2.63850.96

1.50354

0.866356.34

0.521359.79

0.312963.4

0.149663.87

0.0315558.14

-0.0285745.9

-0.0500730.12

71016.01

7207.323

7303.603

7402.149

7501.405

7600.9524

7700.6943

7800.5709

7900.4847

8000.352

8100.1848

8200.06654

8300.02516

8400.0003443

850-0.08556

7(b)

7(b) + SQ2

Sheet1

compound 7bcompound 8compound 10compound 12compound 12co-dyed compound 7b with SQ2

WLQEJsc [mA/cm2]: 7.703058WLQEJsc [mA/cm2]: 9.61WLQEJsc [mA/cm2]: 4.26WLQEJsc [mA/cm2]: 3.74WLQEJsc [mA/cm2]: 3.70Wavelength(nm)QE10.68340 (mA/cm2)

300-4.18E-01-4.18E+01300-2.68E-01300-5.29E-02300-2.47E-013003.82E-01300-2.67E-01-2.67E+01

310-2.42E-01-2.42E+013103.88E-013105.35E-023107.16E-013101.11E+00310-5.65E-02-5.65E+00

320-6.09E-02-6.09E+003206.99E+003202.74E+003208.76E+003209.10E+003205.31E-025.31E+00

3305.45E-025.45E+003302.23E+013301.50E+013302.59E+013302.62E+013301.15E-011.15E+01

3401.11E-011.11E+013403.60E+013403.01E+013404.00E+013404.04E+013401.60E-011.60E+01

3501.63E-011.63E+013504.06E+013503.59E+013504.42E+013504.49E+013501.68E-011.68E+01

3602.39E-012.39E+013603.87E+013603.22E+013603.92E+013604.05E+013601.44E-011.44E+01

3703.64E-013.64E+013703.69E+013702.66E+013703.09E+013703.26E+013701.48E-011.48E+01

3804.97E-014.97E+013803.77E+013802.62E+013802.87E+013803.03E+013802.42E-012.42E+01

3906.07E-016.07E+013903.88E+013902.81E+013903.42E+013903.48E+013903.69E-013.69E+01

4006.75E-016.75E+014004.00E+014003.17E+014004.17E+014004.17E+014004.76E-014.76E+01

4107.25E-017.25E+014104.10E+014103.81E+014104.82E+014104.81E+014105.48E-015.48E+01

4207.51E-017.51E+014204.35E+014204.55E+014205.29E+014205.30E+014206.08E-016.08E+01

4307.58E-017.58E+014304.73E+014305.13E+014305.43E+014305.49E+014306.54E-016.54E+01

4407.57E-017.57E+014405.21E+014405.35E+014405.71E+014405.78E+014406.85E-016.85E+01

4507.55E-017.55E+014505.71E+014505.41E+014505.87E+014505.94E+014507.03E-017.03E+01

4607.52E-017.52E+014606.13E+014605.43E+014605.53E+014605.57E+014607.11E-017.11E+01

4707.49E-017.49E+014706.49E+014705.30E+014704.94E+014704.97E+014707.18E-017.18E+01

4807.51E-017.51E+014806.62E+014804.92E+014804.57E+014804.55E+014807.20E-017.20E+01

4907.57E-017.57E+014906.73E+014904.41E+014904.32E+014904.22E+014907.12E-017.12E+01

5007.58E-017.58E+015006.79E+015003.96E+015003.81E+015003.68E+015006.84E-016.84E+01

5107.54E-017.54E+015106.81E+015103.56E+015103.06E+015102.95E+015106.31E-016.31E+01

5207.43E-017.43E+015206.80E+015203.18E+015202.28E+015202.20E+015205.55E-015.55E+01

5307.17E-017.17E+015306.75E+015302.95E+015301.61E+015301.57E+015304.69E-014.69E+01

5406.60E-016.60E+015406.67E+015402.77E+015401.07E+015401.06E+015403.90E-013.90E+01

5505.65E-015.65E+015506.52E+015502.40E+015506.54E+005506.60E+005503.33E-013.33E+01

5604.46E-014.46E+015606.29E+015601.93E+015603.79E+005603.91E+005602.99E-012.99E+01

5703.24E-013.24E+015705.98E+015701.40E+015702.25E+005702.25E+005702.91E-012.91E+01

5802.17E-012.17E+015805.65E+015808.05E+005801.32E+005801.25E+005803.06E-013.06E+01

5901.36E-011.36E+015905.20E+015903.95E+005907.77E-015906.63E-015903.41E-013.41E+01

6007.98E-027.98E+006004.76E+016001.73E+006002.78E-016006.17E-026003.96E-013.96E+01

6104.60E-024.60E+006104.25E+016101.02E+006101.49E-01610-8.04E-026104.59E-014.59E+01

6202.64E-022.64E+006203.74E+016205.16E-016206.23E-02620-1.66E-016205.10E-015.10E+01

6301.50E-021.50E+006303.24E+016302.51E-01630-1.44E-02630-2.29E-016305.40E-015.40E+01

6408.66E-038.66E-016402.77E+016401.33E-01640-4.54E-02640-2.62E-016405.63E-015.63E+01

6505.21E-035.21E-016502.35E+016508.49E-02650-4.12E-02650-2.45E-016505.98E-015.98E+01

6603.13E-033.13E-016601.95E+016605.81E-02660-3.91E-02660-2.57E-016606.34E-016.34E+01

6701.50E-031.50E-016701.61E+016706.45E-02670-2.90E-02670-2.53E-016706.39E-016.39E+01

6803.16E-043.16E-026801.32E+016806.79E-02680-4.96E-02680-2.55E-016805.81E-015.81E+01

690-2.86E-04-2.86E-026901.08E+016904.97E-02690-7.69E-02690-2.66E-016904.59E-014.59E+01

700-5.01E-04-5.01E-027008.49E+00700-1.35E-02700-9.50E-02700-3.12E-017003.01E-013.01E+01

7106.73E+00710-8.20E-02710-2.97E-017101.60E-011.60E+01

7205.34E+00720-8.04E-02720-2.76E-017207.32E-027.32E+00

7304.15E+00730-9.90E-02730-2.90E-017303.60E-023.60E+00

7403.21E+00740-1.16E-01740-3.25E-017402.15E-022.15E+00

7502.44E+00750-1.27E-01750-3.27E-017501.41E-021.41E+00

7601.81E+00760-1.32E-01760-3.33E-017609.52E-039.52E-01

7701.34E+00770-1.32E-01770-3.25E-017706.94E-036.94E-01

7808.93E-01780-1.67E-01780-4.09E-017805.71E-035.71E-01

7906.35E-01790-1.47E-01790-3.57E-017904.85E-034.85E-01

8004.32E-01800-1.50E-01800-3.54E-018003.52E-033.52E-01

8102.45E-01810-1.82E-01810-4.10E-018101.85E-031.85E-01

8202.37E-01820-8.09E-02820-1.90E-018206.65E-046.65E-02

8302.34E-01830-4.04E-02830-8.91E-028302.52E-042.52E-02

8409.25E-02840-9.26E-02840-2.08E-018403.44E-063.44E-04

850-1.02E-01850-8.56E-04-8.56E-02

860-2.02E-03-2.02E-01

870-2.15E-03-2.15E-01

880-1.47E-03-1.47E-01

890-1.20E-03-1.20E-01

900-1.48E-03-1.48E-01

910-1.67E-03-1.67E-01

920-2.07E-03-2.07E-01

930-3.29E-03-3.29E-01

940-4.90E-03-4.90E-01

950-4.95E-03-4.95E-01

Sheet1

7(b)

8

10

12

7(b) + SQ2

Sheet2

Sheet3

Selective desorption

Holliman et al., RSC Advances, 2014, 4(5), 2515-2522.

Imaging dye uptake (QC)

T.M. Watson, P.J. Holliman and D.A. Worsley, J. Mat. Chem., 2011, 21, 4321-4325.M.L. Davies, T. Watson, P.J. Holliman, A. Connell, D. Worsley, Chem. Comm., 2014, 50, 1251212514.

I3-/ I-

TiO2

Ef

e-

TiO2 on Working

Electrode

Dye

Pt on Counter

Electrode

Electrolyte

Current collection

Electrolyte

SolidHole Transport Materials (HTMs)

LiquidRedox couple

www.dyesol.com

I3-/I- Co2+/Co3+

N N

OCH3 OCH3

OCH3H3CO

N N

OCH3 OCH3

OCH3H3CO

Spiro unit inhibits crystallisation

Matches HOMO to dye

h+

Hole transporter

Absorber

Scaffold (charge carrier)

Light excites absorber creating electron () and hole (h+)

Perovskite operation and architecture

Contact

Snaith et al., Science, 2012, 338, 643.

Planar

Mesoporous scaffolds

Electron () injects into TiO2 and travels to electrode.

Hole (h+) travels through HTL

h+

TiO2 Al2O3

Electron () travels through absorber to electrode.

Hole (h+) travels through HTL

h+

TiO2 Al2O3

Mesoporous scaffolds

Mesoporous TiO2

HTM

Contact

FTO

Compact TiO2

Kim et al. J. Phys. Chem. C, 2014, 118 (11), 5615

MesoporousPlanar

Zhang et al. J. Mat. Chem. A, 2015, 13, 12133

Jsc = 18.27 mAcm-2Voc = 1.01 VFF = 0.77

Record perovskite device (20.8%)

Absorber = FAI + PbI2 + MAI + PbBr2

24.60 mAcm-21.16 V0.73Tress et al., Sci. Adv. 2016, doi: 10.1126/sciadv.1501170

Scaffold = Mesoporous TiO2

HTM = spiro-OMeTAD

FAI is [H2N-CH=NH2]+

MAI is [CH3NH3]+

Au back contact

Substrate cleaning(20 min)

TiO2 BL(1 min)

Sinter @ 450C(30 min)

Drying(5 min)

Mesoporous TiO2(30 min)

Perovskite deposition(1 hour)

Re-sinter@ 450C(30 min)

Working Electrode

Counter Electrode Golddeposition(30 min)

Laminate(5 min)

Perovskite manufacturing

HTMdeposition

(5 min)

Precursor solutions

Perovskite manufacturing

Glass cutting

Glass cleaning

Metal oxide layers

Perovskite deposition

Spin coat deposition onto 100C pre-heated substrates

CH3NH3PbBr3, CH3NH3PbICl2

Perovskite annealing

CH3NH3PbICl2 substrates go from brown in spin coater to pale yellow in first few mins of annealing. Then they turn grey-black

CH3NH3PbBr3

CH3NH3PbICl2

Perovskites retain residual solvent

DMF loss is not linear with T

At < ca. 150 C loose DMF leaves

At higher T, bound or trapped

DMF leaves

Only > 240 C do we see HCl, CH3NH2 Mass Heat FTIR1720

Perovskite annealing

PbCl2 + CH3NH3I CH3NH3PbI3-xClx

Measure DSC and TGA whilst FTIR gives real-time FTIR of evolved gases

A.E. Williams, P.J. Holliman, M.J. Carnie, M.L. Davies, D.A. Worsley, T.M. Watson, J. Mater. Chem. A, 2014, 2, 19338

Bright field optical microscopy of perovskite films (x10)

CH3NH3PbBr3 CH3NH3PbICl2

Hole transport material

Plan viewSpiro-OMeTAD

Device masking and metal back contact deposition

Final devices and device testing

Bryant et al., Adv. Mater., 2014, 26, 7499.

90% at 500nm PET embedded Ni micro-grid Epigem 300s (1.2 /sq)

Laminate back electrode

3. Manufacturing issuesProduct formProcessingScaling

Si Modules

PV processing

Integrating cSi modules

Processing

Laboratory scale (batch)

Commercial scale (roll to roll)

PV Product Form

Roof mounted modules

3rd Generation (flexible PV)

Flexible BIPV

Generate - store - release

Buildings as Power Stations

Shared vision: To functionalise the outside surfaces of buildings ... new and existing.

4. Summary

Grid parity (cost)

End use (efficiency, power density)

Lifetime

Scaling (R2R)

Product form - bespoke PV

Integration

Technology choice?

For DSC 20 year technology = 14%

Liquid to solid (substrates, t) Lifetime (> 5 year) Cost, processing times Commercial (G24Power) Market

For perovskites 4 year technology = 20%

Lead? Out of the dry box Processing solvents Scaling (cells to modules) Lifetime

Where are we now, where next?

Photo-electrodes

Mesoporous TiO2 - = 7.3%. ORegan & Grtzel, Nature, 1991, 353, 24.

Crystalline TiO2 nanoparticles Barb et al., J. Am. Ceram. Soc., 1997, 80, 3157.

Low T sintering Holliman et al., J. Mater. Chem. A, 2014, DOI:10.1039/C4TA01000K.

Dyes

Yellow dye - = 2.6%. Holliman et al., J. Mat. Chem., 2012, 22(26), 13318.

D149 = 8.0. Horiuchi et al., JACS, 2004, 126, 12218.

Panchromatic Black Dye Nazeeruddin et al., Chem. Commun., 1997, 1705.

N719 - = 11.0%. Nazeeruddin et al., J. Am. Chem. Soc., 2005, 127, 16835.

Blue squaraine SQ2 - = 5.4%. Geiger et al., Adv. Funct. Mater., 2009, 19, 2720.

Panchromatic squaraine Maeda, et al. New J.Chem., 2013, 37,71, 701.

Light harvesting

Porphyrin + triarylamine - = 12.3%. A. Yella et al., Science, 2011, 334, 629

Alkoxysilyl carbazole - = 12.0%. Yano et al., Chem. Commun., 2014, 50, 6379.

Silyl linker + coumarin - = 12.8%. Yano et al., Chem. Commun., 2015, 51, 6315.

Silyl linker + LEG4 - = 14.3%. Yano et al., Chem. Commun., 2015, 51, 18894.

Fast processing

5 min dyeing - = 5.0%. Holliman et al., Chem. Comm., 2010, 46, 7256.

Rapid, NIR sintering Worsley et al., Progr. Photovolt. Res. Appl., 19 (4), 482.

DSC Reviews

Hagfeldt et al., Chem. Rev., 2010, 110, 6595.

DSC references

Perovskite architectures

Mesoporous devices - = 15.0%. Snaith et al., Science, 2012, 338, 643.

Planar devices Zhang et al. J. Mat. Chem. A, 2015, 13, 12133.

Perovskite coverage Huang et al., PCCP, 2015, 17, 2015.

Efficiency

= 19.3% Zhou et al., Science, 2014, 345 (6196), 542.

= 20.8% Tress et al., Sci. Adv. 2016, doi: 10.1126/sciadv.1501170

Hysteresis

Solvent processing Jeon et al., Nature Mater., 2014, 13, 897.

Pb-free

Tin perovskites - = 6.0%. Snaith et al., Energy Env. Sci., 2014, 7, 3061.

Perovskite references

Perovskite processing

Solvent safety. Holliman et al., Mater. Res. Innov., 2015, 19, 508.

Thermal analysis Williams et al., J. Mater. Chem. A, 2014, 2, 19338-19346.

Perovskite ink. Jones et al., Chem. Comm., 2016, 52, 4301.

Counter electrodes

Laminate Bryant et al., Adv. Mater., 2014, 26 (44), 7499.

NiO/C Xu et al. NanoLett, 2015, 15, 2402.

Carbon Zhang et al., J. Mater. Chem. A, 2015, 3, 9165.

Carbon Wei et al., Carbon, 2015, 93, 861.

Perovskite Reviews

N.-G. Park, Mater. Today, 2015, 18(2), 65.

Acknowledgements

Bangor Rosie Anthony, Robert Hobbs, Leo Furnell, Sanjay Ghosh, Arthur Connell, Chris Kershaw, Eurig Jones

SPECIFIC (Swansea)Joel Troughton, Daniel Bryant

Slide Number 1Slide Number 2Slide Number 3Slide Number 4Slide Number 5Slide Number 6Slide Number 7Slide Number 8Slide Number 9Slide Number 10Slide Number 11Slide Number 12Slide Number 13Slide Number 14Slide Number 15Slide Number 16Slide Number 17Slide Number 18Slide Number 19Slide Number 20Slide Number 21Slide Number 22Slide Number 23Slide Number 24Slide Number 25Slide Number 26Selective desorptionImaging dye uptake (QC)Slide Number 29Slide Number 30Slide Number 31Slide Number 32Slide Number 33Slide Number 34Slide Number 35Slide Number 36Precursor solutionsGlass cleaningMetal oxide layersPerovskite depositionPerovskite annealingSlide Number 42Bright field optical microscopy of perovskite films (x10)Hole transport materialDevice masking and metal back contact depositionFinal devices and device testingSlide Number 47Slide Number 48Si ModulesSlide Number 50Slide Number 51Slide Number 52Slide Number 53Slide Number 54Slide Number 55Slide Number 564. SummarySlide Number 58Slide Number 59Slide Number 60Acknowledgements