Dye-sensitized nanostructured (fractal) photoanode

J. Desilvestro et al.
J. Am. Chem. Soc. 1985, 107, 2988

Roughness factor = ~ 300

dye-coverage : Γ = 3 ·1016 cm–2
optical cross-section: σ = 5 ·10–17 cm2 ( ε = 1.3 ·104 l· mol–1· cm–1 )
Absorbance : A = Γ · σ = 1.5 [ - ]
Light-harvesting ef ciency : LHE = 1 – 10–A = 0.97
102
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Mesoporous titanium dioxide | electrolyte bulk heterojunction

The term "bulk heterojunction" is used to describe

a heterojunction composed of two different mate-
rials acting as electron- and a hole- transporters,
respectively, which are mixed together in a bulk
and thus containing several discrete interfaces.

0.1 µm

B. O'Regan & M. Grätzel,

Nature 1991, 353, 737 103
Dye-sensitized nanocrystalline solar cells (DSSC)

The mesoporous TiO2

photoanode in DSSCs is made e- e-
of typically 10-15 nm-radius
(S+/S*)
nanocrystalline particles, whose e-
A
dimensions are smaller than the
e-
typical Debye length charac- e-
terizing this material. As a
consequence, no space charge TiO2
Pt
layer exists inside the particles ΔU
and no electric eld is formed hν
at the oxide/ adsorbed dye (D+/D) e-
layer interface that could help
separating photogenerated e-
charges. The prevention of the
carriers recombination (back (S+/S)
electron transfer) must then
rely on the kinetic competition
between the various forward SC = TiO2
and back electron transfer S = redox dye-sensitizer
processes (see next page). D = redox mediator
104
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Kinetic competition between ET processes in DSSC

Photoexcitation:
hν
(S+/ S*) S | SC S*| SC
e–
200 fs
~ 1 ps Charge injection:
cb S*|SC e– (SC) + S+|SC
hν 35 fs - 15 ps
15 ns
Dye regeneration:
e– e– S+|SC + D S|SC + D+
(D+/ D )
0.1 - 30 µs

e– Charge recombination:
S+| SC + e– S | SC
(S+/ S ) 0.2 - 0.8 ms

Dark current:
TiO2 Dye-sensitizer Mediator
D+ + e– D
10 ms

105
 Dye-sensitized nanocrystalline solar cells (DSSC)

DSSC Basics
• Cell ef ciency = 10-12
• Module ef ciency = 6-9
• 0.3 year payback period
(32 kWh/m2) / [(1700 kWh/
m2· yr) * 0.06]

Advantages of DSSC
• Much less sensitive to angle of incidence (good in diffuse light
• Can be designed for operation at very low light level
• Ef ciency is optimal at low light intensity of scattered ligh
• Wide range of optimal temperature
• Much less sensitive to partial shadin
• Manufacturing is cheap and easy, needs only commonly available processing
equipmen
• Signi cantly lower embodied energy than other solar cells 106
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t

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:

 DSSC vs Si cells under low light intensity

Electron-hole recombination in Si and GaAs homojunction cells takes place essentially

upon prior trapping of carriers. If the density of photogenerated carriers is low compared
to the trap density (under low light intensity), recombination is very effective and the
conversion ef ciency thus tends to 0. Under high light intensities, trap states are lled up
by the rst carriers and recombination is minimized. As a result, conversion yields for such
systems are generally higher under strong light irradiation.

Ef ciency of DSSC under

high light intensities is
often limited by the
conduction of the hole
transporting material
DSSC (ion transport in the
electrolyte). Their
conversion ef ciency
tends then to be
maximum under
moderate incident light
intensity (1/10 Sun).

107
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From DSSCs to double donor-acceptor heterojunction photovoltaic cells

ETM Absorber HTM

–3.5

–4.0
Energy [eV / vacuum ]

spiro-MeOTAD
CH3NH3PbI3-xClx

CH3NH3PbI3
ZnO

TiO2
PCBM

PCPDTBT
–4.5

1.2 V

Au
CuSCN
N719

P3HT
FTO

–5.0

–5.5

–6.0

109
Solid-state double donor-acceptor heterojunction: Perovskite solar cells

A. Marchioro, J.-E. Moser et al.

Nature Phot. 2014, 8, 250

spiro-TAD HTM

MAPI perovskite

TiO2

108
 level diagram of Tang’s cell. When the cell is illuminated, CuPc (electron donor) absorbs
photons, forming excitons, which then diffuse to the interface between CuPc and PV
(electron acceptor). Since PV has a significantly larger electron a⇤nity, the injection
Organic photovoltaics
of electron from the LUMO (OPV)level of CuPc to the LUMO level of PV is energetically
favorable. The electron transfer from CuPc to PV can be regarded as a photo-excited
redox reaction. The improved photovoltaic performance showed that this redox reaction
is Donor-acceptor bilayer
more e⇤cient in breaking cells than the built-in field in single layer devices.
excitons

metal
Metal electrode
Electrode
Energy

LUMO
LUMO

V
electron
Electron 4
metal acceptor
Donor
Metal 3
electrode
Electrode
2
electron
Electron 4
transparent
Transparent
HOMO donor 1
Acceptor
electrode
electrode
HOMO
transparent
Transparent
electron
Electron electron
Electron incident
Incident electrode
Electrode
donor
Donor acceptor
Acceptor light
Light

(a) (b)

C. W. Tang 1) Exciton formation ; 2) Exciton diffusion

Fig. 2.16: (a) Energy diagram of a typical organic solar cell; (b) photo-induced charge separation
Appl. Phys. Lett. 1986, 48, 183 3) Charge separation ; 4) Charge transport
in an organic solar cell: 1) formation of exciton; 2) exciton diffusion; 3) exciton
separation; 4) drifting of separated charges.
109

 Organic donor-acceptor bulk heterojunction

A
metal electrode - -
electron-hole

selectiv
injection

exciton
glass or
polymer hν hν
nanostructured transparent electron-donor electron-acceptor
bulk metal-oxide material material

Electron-donor material combines three functions

1) light absorption, 2) exciton conduction, and 3) hole transport

110
e

Conjugated polymer ('plastic') solar cells

Conjugated polymers are excellent candidates

fo r u s e i n l ow - c o s t e l e c t ro n i c s a n d
photovoltaics. Polymer-based solar cells have
reached power conversion ef ciencies of 6% in
recent reports. Deposition of organics by
screen printing, doctor blading, inkjet printing,
and spray deposition is possible because these
materials can be made soluble. These
techniques are required for the high-
throughput roll-to-roll processing that will
drive the cost of polymer-based PV down to a
point where it can compete with current grid
electricity. Additionally, these deposition
techniques all take place at low temperature,
which allows devices to be fabricated on plastic
substrates for exible devices. 111
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Small molecule-based OPV

h+
e–

F. A. De Castro et al.
Phys. Chem. Chem. Phys.
2009, 11, 8886-8894
112
 Convergence of 1st, 2nd and 3rd generation photovoltaic technologies

p-n junction: Si, GaAs(1G) OPV : polymer, DSSC : liquid electrolyte,

Thin- lm CIGS, CdTe (2G) small molecule-based (3G) solid HTM-based (3G)

p-doped n-doped donor acceptor HTM dye TiO2

cb e– e– e–

EF,n* cb
EF,n* EF,n*

hν –F·∆U hν –F·∆U hν –F·∆U

EF,p* EF,p* EF,p*

vb
Evolution
h+
of Silicon Solar hCell
+
Design
h+

metal nger hν coating ITOsiliconhν hν

Space cellinjection
design layers F-doped SnO2
developed
in the early 1960s, which became a
standard design for over a decade.
n-type donor acceptor dye-sensitized TiO2

Pt
p-type
p-type metal noble
contact metal HTM
113
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