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Solar Photovoltaics & Energy Systems Parts 8. Dye sensitized solar cells ChE-600 Kevin Sivula, Spring 2012

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Page 1: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Solar Photovoltaics & Energy Systems Parts 8. Dye sensitized solar cells ChE-600 Kevin Sivula, Spring 2012

Page 2: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Averaged Solar Radiation 1990-2004

Assuming 8% energy conversion efficiency

Page 3: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Thin Film performance overview

Page 4: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Installed capacity of photovoltaics

http://www.ren21.net/Portals/97/documents/GSR/REN21_GSR2011.pdf

Page 5: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

x-Si approaches grid parity

Without a significant paradigm shift in fabrication

Page 6: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

“Generations” of solar cells

Page 7: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

A new paradigm for solar energy conversion

7

} Low cost processing } Roll-to-roll compatible } Solution processing } Atmospheric pressure } Avoid high temperatures

Paint Cost = $1/m2

} High conversion efficiency } High stability

} Low to medium purity materials } Solar light absorption } Transport of electric charge

Page 8: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Natural photosynthesis

Page 9: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Light harvesting

cryptoxanthin

Page 10: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Molecular orbitals review

Elec

tron

ene

rgy

HOMO

LUMO

Page 11: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Molecular orbitals review

Page 12: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Molecular orbitals review

Page 13: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Metal-organic dyes and pigments

Page 14: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Excitation of a molecular absorber

Electron energy

Excited state (S*)

Ground state (S°)

Light energy (hν)

Dye molecule

e-

Chemical Structure of N3 Dye

Conditions for molecular absorption: 1. hν = S* - So

2. The transition dipole

moment is not zero

for a transition between an initial state, n, and a final state, m

Page 15: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Excitation of a molecular absorber

Electron energy

Excited state (S*)

Ground state (S°)

Light energy (hν)

Dye molecule

e-

S° + hν → S* (excitation) S*→S° (deactivation) 50 ns Chemical Structure of N3 Dye Ground state (S°)

Excited state (S*)

Page 16: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Capturing the excited state with a DSC

1. Light absorption 2. Injection to

semiconductor

-0.5

0

0.5

TiO2

1.0

S*

S°/S+

hν

Dye Electrolyte

Ox Red

Cathode

1

2 -1.0

e-

Wide band-gap semiconductor

e-

Elec

tron

ene

rgy

(eV

vs. N

HE)

Page 17: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Physics of electron transfer

Page 18: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Ultrafast electron injection

Ground state (S°)

Excited state (S*)

Page 19: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Capturing the excited state with a DSC

1. Light absorption 2. Injection to

semiconductor 3. Percolation 4. Regeneration of

oxidized species 5. Regeneration of

oxidized dye

-0.5

0

0.5

TiO2

1.0

S*

S°/S+

hν

Dye Electrolyte

Ox Red

Maximum Voltage

Cathode

LOAD

e-

External circuit

1

2 3

4

5

-1.0

e-

Wide band-gap semiconductor

Elec

tron

ene

rgy

(eV

vs. N

HE)

Page 20: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

The DSC vs. Conventional pn junction PV

TiO2

Dye

Electrolyte

Cathode

+

n-type Silicon

p-type Silicon

+ +

+ +

• Charge carriers (excited electrons) are produced throughout the semiconductor • Semiconductor considerations:

• Precise doping • high purity • high crystalinity

• Light absorption and charge transport are decoupled • Relaxed constraints on individual components (each can be separately tuned) • Only monolayer of dye on TiO2

Page 21: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Device characterization metrics

IPCE(λ) = = habs Fcg hcoll

hab: light harvesting efficiency

Fcg: quantum yield of charge carrier generation

hcoll = efficiency of charge carrier collection

Electrons out

Photons in

PCE or ηPCE = = JSC : Short circuit current density

VOC : Open circuit voltage

FF: Fill factor

Max. power out

Power in

JSC VOC FF

Ilight/A

JSC

VOC

max (J·V) JSC VOC

FF =

Page 22: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

22 Solar intensity mW cm-2

Pow

er c

onve

rsio

n ef

ficie

ncy

%

Single crystal silicon cell

Dye sensitized cell

Dye sensitized solar cells outperform silicon at lower light levels

Higher open circuit voltage at low light intensity gives dye cell better performance in diffuse daylight

Page 23: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

History of the Dye Sensitized solar cell

Page 24: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

mesoscopic photoelectrochemial

cell

100 nm

highly efficient sensitization of

TiO2 nano-crystals

B.O’Regan and M. Grätzel, Nature 1991,

353, 737

1985 1988 1991 2006 2010

Page 25: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Mesoscopic structure is critical

25

TiO2

Dye

Electrolyte

Anode

Cathode

Page 26: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

IPCE = electrons out

photons incident

Single crystal TiO2

Nanocrystalline anatase TiO2

Dye monolayer on Single crystal TiO2

Dye Sensitized Mesoporous anatase TiO2

( <101> anatase)

Benefits of the nanostructure

Page 27: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

• Surface area • Photoinduced conductivity • Charge carrier screening

100 nm IPCE =

electrons out photons incident

Single crystal TiO2

Nanocrystalline anatase TiO2

Benefits of the nanostructure

Page 28: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

• Surface area • Photoinduced conductivity • Charge carrier screening

H.G. Agrell, G. Boschloo, A. Hagfeldt J. Phys. Chem. B 2004, 108, 12388

IPCE = electrons out

photons incident

Single crystal TiO2

Nanocrystalline anatase TiO2

Benefits of the nanostructure

Page 29: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

• Surface area • Photoinduced conductivity • Charge carrier screening

Electrons in TiO2 Surrounding electrolyte

ENHE

-0.5

0

0.5

TiO2

1.0

Electron diffusion

No space-charge Layer at TiO2 - electrolyte interface

CB

IPCE = electrons out

photons incident

Single crystal TiO2

Nanocrystalline anatase TiO2

Benefits of the nanostructure

Page 30: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Redox couple selection

-0.5

0

0.5

TiO2

1.0

S*

S°/S+

hν

Dye Electrolyte

Ox Red

LOAD

e-

External circuit

1

2 3

4

5

-1.0

e-

Wide band-gap semiconductor

Elec

tron

ene

rgy

(eV

vs. N

HE)

Page 31: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

20 nm TiO2 particles +

400 nm TiO2 particles

Optical Engineering with Advanced Nanostructures

20 nm TiO2 particles

Page 32: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

G. Rothenberger et al. Solar Energy Materials & Solar Cells 58 (1999) 321 Hore S, Vetter C, Kern R, et al. Solar Energy Materials & Solar Cells 90 (2006) 1176

20 nm TiO2 particles +

400 nm TiO2 particles

Optical Engineering with Advanced Nanostructures

Page 33: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Engineering the dye

M.K. Nazeeruddin et al., J. Am. Chem.Soc. 123, 1613, (2001)

N749 tri(cyanato)-2.22-terpyridyl-4,44-tricarboxylate)Ru(II)

N3 cis-Ru(SCN)2L2

(L = 2,2-bipyridyl-4,4-dicarboxylate)

NN

NN

RuN

N C S

C SO

OH

OHO

HO

O

O OH

NN

NN

RuN

N C S

C SO

O-

HO

O

O O-

CS

3- [(C4H9)N]3+

Page 34: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Record high conversion efficiencies

Page 35: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Need to increase band width of light absorption

} Difficult to construct dye with pan-chromatic light absorption } Organic dyes } Porphyrin-based dyes

Yum et. al. J. AM. CHEM. SOC. 2007, 129, 10320-10321

Cid et. al. Angew. Chem. Int. Ed. 2007, 46, 8358 –8362

Page 36: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

NN

NN

RuN

N C S

C SO

OH

OHO

HO

O

O OH

NN

NN

RuN

N C S

C SO

OH

HO

O

O OH

CS

NN

NN

Ru

O

OH

OHO

HO

O

O OH

N

N

OH

O

O

HO

Altering the colors absorbed and transmitted

Page 37: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

37

Page 38: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

38

Page 39: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

39

Page 40: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Device Stability

The sensitizer has to sustain 100 million cycles during 20 years of outdoor cell operation

To reach 100 million turnovers branching ratios of kInj/k1 and kreg/k2 > 108 are required

0

Page 41: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Device Stability

41

The sensitizer has to sustain 100 million cycles during 20 years of outdoor cell operation

To reach 100 million turnovers branching ratios of kInj/k1 and kreg/k2 > 108 are required

0

Page 42: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Light soaking at 2.5 suns (2.5kW/m2)

DSC masterplates

Requirements for outdoor use according to international PV standards applied to single crystal silicon but so far not to thin film PV cells Light soaking (full sun 55-60 C): 1000 hours Heat stress at 85 C: 1000 h Hot humidity test (85%/85C) and temperature cycling

Device Stability

Page 43: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

The C101 sensitizer maintains outstanding stability at efficiency levels over 9 percent under light soaking at 60oC using a low- volatility electrolyte

Page 44: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

The present status of dye sensitized solar cells

• Power conversion efficiency measured under AM 1.5 sunlight: laboratory cells 12 %, modules 9.5 % (Sony), tandem cells 16%

• stability > 20 years outdoors (DYESOL)

• energy pay back time: < 1 year (3GSolar and ECN, life cycle analysis)

• ease of building integration • transparency and multicolor option (for power window application) • Flexibility • light weight • low production cost • feedstock availability to reach terawatt scale • short energy pay back time (< 1 year) • enhanced performance under real outdoor conditions • bifacial cells capture light from all angles • tandem cell configurations boost efficiency over 15 % • outperforms competitors for indoor applications • Industrial development: roll to roll mass production and commercial sales of light

weight flexible cells started in Cardiff Wales by G24 Innovation (www.g24i.com.)

http://www.g24i.com
http://www.g24i.com
http://www.g24i.com
Page 45: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

The G24I plant in Cardiff has started production on June 21 (solstice),2007

Page 46: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

46

Page 47: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

The first G24I product is a light weight flexible power supply for portable electronics

Page 48: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

48

Page 49: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

The beauty of a dye-sensitized Walkman

Page 50: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

Solar Powered Solar Panel Sun Glasses The SIG, or “Self-Energy Converting Sunglasses” are quite simple. The lenses of the glasses have dye solar cells, collecting energy and making it able to power your small devices through the power jack at the back of the frame. “Infinite Energy: SIG”

Page 51: Solar Photovoltaics & Energy Systems...7 }Low cost processing }Roll-to-roll compatible }Solution processing }Atmospheric pressure }Avoid high temperatures Paint . Cost = $1/m. 2} High

mesoscopic photoelectrochemial

cell

highly efficient sensitization of

TiO2 nano-crystals

B.O’Regan and M. Grätzel, Nature 1991,

353, 737

Mass production

1985 1988 1991 2009 2005

Scale up to modules

tomorrow


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