Optimizing Dyes

Optimizing Dyes for

for
DSSC
DSSC

Soong Sil Unversity

Yang Ju Hee
environmental

Oil KILLs man

Dye-Sensitized Solar Cells Silicon-Based Solar Cell

• Relatively inexpensive • Expensive
– Made in non‐vacuum setting mainly at 
g y – Made in high vacuum at high heat
g g
room temperature – High manufacturing costs
– Relatively simple manufacturing  • Need TLC
process
– Fragile, rigid, thick 
Fragile rigid thick
• Need little TLC
• Long return on investment
– Thin, lightweight, flexible
– Takes 4 years to produce energy 
• Short return on investment savings equivalent to cost of
savings equivalent to cost of 
– Takes approx 3 months to produce  production
energy savings equivalent to cost of 
production
Factor

•Dye 
y
•Electrolyte 
•HTM
•Metal oxide
 g p
Two glass plates Titanium dioxide
Titanium dioxide Dye
y

Counter / C Electrolyte Drive

www.vicphysics.org/documents/events/stav2004/Physics_A12_dsc.ppt ‐
 the most efficient DSSCs show efficiencies of over 10%
Problem
•Use an HTM comprising an I‐/I3‐ redox electrolyte 
Solution
q
•Volatile solvent  requires the cells to be sealed
•I‐/I3‐ redox electrolyte can be corrosive towards 
the Pt electrode.

Alternative

G l l t l t t ( 6%)
•Gel electrolyte system (η=6%)
•Organic HTM system (η=4%)
Ionic liquid system (η
•Ionic liquid system (η=8%)
8%)
Dye

Organomaetallic dye

•Charge separation from Ru metal to ligand(Ru‐bpy) 
and from ligand
and from ligand to
to Ru
Ru metal(SCN
metal(SCN‐Ru) 
Ru)

O
Organic
i dye
d

•Electro donor and electron acceptor group

•Electro donor and electron acceptor group
•Spacer(π‐congugation) group
gg p
•Anchoring group
Dye
HOOC

COOH
[{(4 4’ CO2H)2(bipy)}
[{(4,4’‐CO (bi )}2RuX
R X2]
N
X N
(bipy=2,2’‐bipyridyl; X=Cl, Br, I, CN, NCS)
Ru
X N
N
COOH

COOH
MLCT

Ru dye 6‐chelating organic metal compound

eg

t2g

Tunning MLCT

•Using ligand of lowing π* molecular orbital

•Using strong electro‐aceptor ligand
 Functional group

Bind strongly to TiO2

•To ensure efficient electron injection into the TiO2 conducting band
•To prevent gradual leaching by the electrolyte
Carbo lic acid Phosphoric acid
Carboxylic acid Phosphoric acid
•Enhancing molar extinction coefficients

Thi
Thiocyanato(-NCS)
t ( NCS) ligand
li d

• controlling  t2g
controlling t2g orbital
• Electron transmission from electrolyte to dye
Must
Have
Have_____

• bi
bindd strongly
l to TiO2 byb means off an anchoring
h i group
• The LUMO of the dye must be sufficiently high in energy
for efficient charge injection into the TiO2
• The HOMO must be sufficiently low in energy for
efficient regeneration of the oxidized dye by the HTM
• Absorb solar radiation strongly with absorption bands in
the visible or near
near-IR
IR region
• Electron transfer from the dye to the TiO2 must also be
p in comparison
rapid p with decayy to the g
ground state of
the dye

Ref. ; J. AM. CHEM. SOC. 2005, 127, 3456-3462

N3

J. Am. Chem. Soc., Vol. 115, No. 14, 1993 6385
Black dye

y y g y y
•N3 ruthenium dye carrying only one corboxylated bipyridyl
py y
ligand
•Low adsorption of dye
High photovoltaic conversion
•High photovoltaic conversion
efficiency

ACCOUNTS OF CHEMICAL RESEARCH / VOL. 33, NO. 5, 2000
N719

•contains protonated carboxylic groups

•contains protonated carboxylic groups
•Adsorption the anchoring groups transfer most of their protons 
to the TiO2 surface charging it positively by the Fermi level 
moves down
d

C h e m . C o m m u n . , 2 0 0 4 , 3 6 2 – 3 6 3
N719
efficiency

Inorganic Chemistry, Vol. 44, No. 20, 2005
Influence of Protons

J. Phys. Chem. B 2003, 107, 8981‐8987
Z955
•linker from carboxylic to phosphoric acid groups
•a blue shift of the absorption maxima
•a blue shift of the absorption maxima
•good stability of the device
•slower charge‐recombination

Z907

Z955
9
Solvent‐free
Ionic liquid

J. Phys. Chem. B, Vol. 108, No. 45, 2004
N845

synthetic
(i) DMF, 4‐[4‐(N,N‐di‐p‐anisylamino)phenoxymethyl]‐
4’‐methyl‐2,2’ bipyridine,90°C
(ii) 4,4’‐dicarboxy‐2,2’‐bipyridine,150°C
(iii) NH4NCS, N
(iii) NH NCS N2, DMF
DMF

•The positive charge is transferred from the ruthenium ion to the 
triarylamine group
T i l i function; hole‐trapping
•Triarylamine f ti h l t i

Chem. Eur. J. 2004, 10, 595 ± 602
Z907

synthetic

(i) DMF,dnbpy,70°C,N2,4 h.
(ii) H2dcbpy 150°C
(ii) H2dcbpy,150 C,N
N2,4 h.
4h
(iii) NH4NCS,150°C,N2,4 h.

[RuCl2(p‐cymene)]2

•Attached hydrophobic chains
E ll bili to both prolonged thermal stress and light 
•Excellent stability b h l d h l d li h
soaking.

Nat.mater. 2, 402,2003
Z907
Stability

efficiency

Nat.mater. 2, 402,2003
K19
•Solvent‐free electrolytes has made striking 
advances
•Increase in extinction coefficient
•A red shift of the maxima of the MLCT band 
was observed
was observed
•relates to extending the spectral coverage 
of the dye

efficiency Stability
bili

J. AM. CHEM. SOC. 2005, 127, 808‐809
Summary

Advances in OptoElectronics Volume 2007, Article ID 75384, 13 pages
Trend

efficiency

S.‐R. Jang et al. / Solar Energy Materials & Solar Cells 91 (2007) 1209–1214
Th k you
Thank