Dye-sensitized and Perovskite Solar Cells | Peter Holliman, University of Bangor
Transcript of Dye-sensitized and Perovskite Solar Cells | Peter Holliman, University of Bangor
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Dye-sensitized and perovskite solar cells
Image:- NASA
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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 [email protected]
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1. Introduction
PV landscapeTechnology choice
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92 elements
Crust - 2 x 1022 kg
Atmosphere - 5 x 1018 kg
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Emissions
An estimated 4,267 deaths (2008)Up to 9% of deaths due to airborne pollution (2012)
London
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More solar energy falls on the Earths surface every day than the whole of humankind could consume in 27 years.
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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
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Geography
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Source:- National Renewable Energy Laboratory (US)
2. Device architecture and operation
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2. Device operation & architecture
Dye-sensitized solar cellsPerovskites
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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
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I3-/ I-
TiO2
Ef
Reverseillumination
e-
TiO2 on Working
Electrode
Dye
Pt on Counter
Electrode
Forwardillumination
Electricity
Electrolyte
Voc
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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
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TiO2 Working Electrode
I3-/ I-
TiO2
Ef
e-
TiO2 on Working
Electrode
Dye
Pt on Counter
Electrode
Electrolyte
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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
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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
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Why a binder?Printed
Sintered
The blancmange effect!
TiO2SolventBinder
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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%
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Absorber
I3-/ I-
TiO2
Ef
e-
TiO2 on Working
Electrode
Dye
Pt on Counter
Electrode
Electrolyte
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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)
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Light harvesting
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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+
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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
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Dye time lapse (60x)
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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
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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
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Selective desorption
Holliman et al., RSC Advances, 2014, 4(5), 2515-2522.
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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.
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I3-/ I-
TiO2
Ef
e-
TiO2 on Working
Electrode
Dye
Pt on Counter
Electrode
Electrolyte
Current collection
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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
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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
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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
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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
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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)
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Precursor solutions
Perovskite manufacturing
Glass cutting
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Glass cleaning
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Metal oxide layers
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Perovskite deposition
Spin coat deposition onto 100C pre-heated substrates
CH3NH3PbBr3, CH3NH3PbICl2
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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
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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
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Bright field optical microscopy of perovskite films (x10)
CH3NH3PbBr3 CH3NH3PbICl2
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Hole transport material
Plan viewSpiro-OMeTAD
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Device masking and metal back contact deposition
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Final devices and device testing
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Bryant et al., Adv. Mater., 2014, 26, 7499.
90% at 500nm PET embedded Ni micro-grid Epigem 300s (1.2 /sq)
Laminate back electrode
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3. Manufacturing issuesProduct formProcessingScaling
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Si Modules
PV processing
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Integrating cSi modules
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Processing
Laboratory scale (batch)
Commercial scale (roll to roll)
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PV Product Form
Roof mounted modules
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3rd Generation (flexible PV)
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Flexible BIPV
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Generate - store - release
Buildings as Power Stations
Shared vision: To functionalise the outside surfaces of buildings ... new and existing.
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4. Summary
Grid parity (cost)
End use (efficiency, power density)
Lifetime
Scaling (R2R)
Product form - bespoke PV
Integration
Technology choice?
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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?
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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
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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.
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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