1 Organic photovoltaic cells polymeric solar cells [email protected] NIS Colloquium – Torino 23 Giugno 2008
1
Org
anic
phot
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2
Ism
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ph
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Org
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NIS
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4
outl
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IS C
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Tor
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23 G
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Why
poly
mer
ic s
olar
cel
ls
Wor
king
pri
ncip
les
The
stat
e-of
-the-
art
New
phot
oact
ive
mat
eria
ls: th
e ke
y fo
r pr
ogre
ss
Con
clus
ions
and
per
spec
tive
s
5
Con
juga
ted
poly
mer
s: s
emic
onduc
tors
& p
last
ics
conductelectricity
Absorband emitlightchromism
easy processability
forth
e d
isco
very
and
deve
lopm
ent
of
cond
uctive
polymers
.
2000 N
obel Pr
ize in
Chemistr
y
Plast
ics
elect
ronics
-lo
wpe
rfor
man
ces
-mod
erat
e m
inia
turi
sati
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ergy
-Low
cost
(phot
olit
hig
rapy
, in
k-je
tpr
inti
ng, ro
ll-t
o-ro
ll)
NIS
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ium
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6
Plas
tic
elec
tron
ics
Ole
d-d
ispl
ays
Sol
arce
llstr
ansi
stor
s
199
0
light
curr
ent
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dev
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arch
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ture
199
519
93
NIS
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loqu
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7
Sem
icon
duc
ting
and m
etal
lic
poly
mer
s
“Ink
s”w
ith
elec
tron
icfu
ncti
onal
ity
Plast
ic s
ubst
rate
Solar
cells
Fun
ctiona
links
NIS
Col
loqu
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orin
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8
Poly
mer
icso
lar
cells
: th
e ad
vant
ages
•Li
ght
wei
ght
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lexib
ility
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emi-
tran
spar
ency
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our
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asti
cs t
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logy
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scal
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ll to
rol
l or
ink
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pri
ntin
g )
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w e
nerg
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nsum
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Low
env
iron
men
tal im
pact
•
Low
inv
estm
ents
•M
ater
ials
eas
ily a
vailab
le
low
cos
t te
chno
logy
and
unc
onve
ntio
nal
appl
icat
ions
NIS
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9
ww
w.k
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om
ww
w.h
ertz
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gber
g.co
mF
.C. K
rebs
etal
s. S
ol. E
nerg
yM
ater
.,Sol
. Cel
l. 9
0, 10
58
(2
00
6)
Poly
mer
ic s
olar
cel
ls: po
ssib
le a
pplica
tion
s•S
tate
of
the a
rt.
eff
. ∼ ∼∼∼
5%
��co
nsum
ables
cons
umables
•re
mot
e ap
plic
atio
ns
NIS
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10
1.Ph
oton
abso
rption
2.Charg
eph
otog
ene
ration
3.tr
ans
port
toth
e e
lect
rodes
Charg
e p
hot
ogene
ration
in o
rganic
mate
rials is
rath
er
poor
+
Phot
oind
uced
char
getr
ansf
er
S
S
S
S
S
R
R
R
R
R
S
R
e-
+
-
S
S
S
S
S
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R
R
R
R
S
R
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+
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S
S
S
S
S
R
R
R
R
R
S
R
e- e-
+
-
Phot
ovolta
iceff
ect
Ene
rgy
leve
ls
DA
How
they
wor
k
light
curr
ent
D
e-
h+
gla
ss
/ p
lastic
anod
o tr
aspa
rent
e
cath
ode
org.
phot
o-ac
tive
laye
r+
-
dev
ice
stru
ctur
e
NIS
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11
Zn
Pc
: d
on
or
MP
P : a
cce
pto
r
C.W
. Tang, Appl.Phys. Lett.
48(1986)183
η= 0
.47
AM
1.5
890 W
/m2
•Abso
rban
ce
•Mis
mat
chto
sola
rsp
ectr
um
abso
rban
ce
☺ ☺☺☺☺ ☺☺☺
The
firs
t or
gani
cso
lar
cell
NIS
Col
loqu
ium
–T
orin
o2
3 G
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008
12
Mol
ecul
ar o
rgan
ic s
olar
cel
ls: D
/A b
ilay
ers
Zn
Pc
: d
on
or
MP
P : a
cce
pto
r
C.W
. Tang, Appl.Phys. Lett.
48(1986)183
η= 0
.47
AM
1.5
890 W
/m2
ITO
vetro
pedot:pss
CuPc
C60
BCP
Al
Cu
Pc
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on
or
C60
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cce
pto
r
BC
P:
e-t
rans.
(bath
ocupro
ine)
η= 3
.6 %
AM
1.5
P. PeumansAppl. Phys. Lett.,
79 (2001), 1268
The
firs
t or
gani
c so
lar
cell
The
evol
utio
n
NIS
Col
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ium
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008
Bul
k het
eroj
unct
ions
wor
k bet
ter
!!
13
DA
e-
h+
gla
ss / p
lastic
Bi-layer
bulk
Donor/Acceptorheterojunction
1 111
- ++-
- + 2 2223 333
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rgy
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hor
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rcui
t
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e
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ode
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e-
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lastic
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OPV
arc
hit
ectu
re
C. J
. B
rab
ec,A
dv.
Fun
ct. M
ater
. (20
01)
11,1
5
14
bul
k het
eroj
unct
ion
sola
rce
lls
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catodo
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k het
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com
posi
te lay
er
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oind
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D:A
char
getr
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nd s
epar
atio
n
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o-sc
ale
phas
ese
greg
atio
n
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bi-
cont
inuo
usne
twor
k
•p, n
mob
ility
phot
oact
ive
phot
oact
ive
mate
rial
mate
rial
The
des
ign
of t
he
phot
oact
ive
mat
eria
l has
a
cent
ral ro
le f
or e
ffic
ienc
y im
prov
emen
ts
NIS
Col
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orin
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008
15
Mat
eria
lsfo
rbul
k het
eroj
unct
ion
Con
juga
ted
don
or p
olymers
acc
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ors
PCBM
perileni
PF1CVTP
MDMO-PPV
APFO-GREEN
P3HT
Nat
ure
mat
eria
ls
vol6
, 49
7 (
20
07)
C71-PCBM
eff.
5.5
%
eff.
5 %
NIS
Col
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ium
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008
16
LUMO
HOMO
t < 100 fs
t >1 ms
Polimero: donatoreFullerene: accettore
N.S. Sariciftcietals. Science
(1992), 258, 1474 S. Morita
als. SolidState Comm.(1992) 82,249
C.J.Brabec
etals. Chem. Phys. Letts(2001) 340 , 232
Tra
sferiment
o di ca
rica
ultr
ave
loce
tra
il po
limero
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iuga
to
foto
ecc
itato
ed il fu
llere
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ati c
arich
i meta
stabilico
nte
mpi
di vita
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Tra
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400
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nerg
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als.
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PCB
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1 (2
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Spe
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phot
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uced
char
getr
ansf
er
NIS
Col
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18
Ass
embla
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di un
a ce
lla s
olar
e po
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vetr
o
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PED
OT
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S
Film
att
tivo
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00
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(10
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m)
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etchinge pulizia
Coatingcon un hole
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PEDOT:PSS
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attivo
Evaporazione
dell’elettrodo
caratt. in luce bianca
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ossigeno
Exte
rnal
Qua
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EQE (%)Wavelength (nm)
dry
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NIS
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19
Phot
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met
ers
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en c
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e
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Wavelength (nm)
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NIS
Col
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20
D/A
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k hete
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NIS
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21
mor
phol
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requ
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Nano
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phase
phase
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Ordered bulk
NIS
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22
Sol
ubilit
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sues
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48
9
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pres
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NIS
Col
loqu
ium
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orin
o2
3 G
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008
24
mor
phol
ogy
vsso
lven
t
S. E
. S
hah
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et
al.A
pplP
hys.
Let
t, 7
8, 8
41
(20
01)
.
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1:4
25
The
stat
e of
the
art
P3H
T:P
CB
M b
ulk
het
eroj
unct
ions
el. d
onor
, p
sem
icon
d.
UV
-Vis
400
600
800
100
01
200
1400
nm
sola
rsp
ectr
um
Mor
pholog
yM
orph
olog
yOpt
imisation
Opt
imisation
App
lA
ppl . . Ph
ysPh
ys. . Le
tt.
Lett
.8
78
7, 0
83
50
6 (
20
05
), 0
83
50
6 (
20
05
)
Adv
Adv .
. F
unct
Fun
ct. . M
ater
Mat
er. . 15
15
16
17 (
20
05
)16
17 (
20
05
)
Nat
ure
Nat
ure
Mat
eria
lsM
ater
ials
448
64
(2
00
5)
86
4 (
20
05
)
η∼ ∼∼∼
5 %
D:A
com
posi
tion
, th
ermal
ther
mal
anne
aling
anne
aling,
dep
osit
ion,
m
olec
ular
wei
ght,
pol
ymer
puri
ty…
…..
el.a
ccep
tor,
n s
emic
ond.
+
bef
ore
20
05
:
η∼
1-2
%
Ther
e is
roo
m t
o re
ach ∼ ∼∼∼
7.5
%
NIS
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26
P3H
T:P
CB
M:
opti
mis
atio
nby
ther
mal
anne
alin
g1:
1 w
:w, c
hlor
oben
zene
, 12
0 °
C
0
10
20
30
40 3
00
400
500
600
700
800
not
anne
aled
4 m
in. an
n.
EQE (%)
Wavelength (nm)
EQ
E: (
nr. e
lett
roni
/nr
foto
ni inc
. )
00.2
0.4
0.6
0.8
1current density (mA .cm
-2)
Voltage (
V)
-55
10
-100
I-V
cur
ves
(whit
elig
ht,
1 s
un)
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9 300
400
500
600
700
800
not
ann
ealed
4 m
in.
30 m
in.
90 m
in.
Wavelength (nm)
Optical density
UV
-Vis
vsan
neal
ing
tim
e
5 µ
m
Opt
ical
mic
rosc
opy R.C
ugol
a,et
als,
Thi
nS
olid
Film
s, 5
11-5
12 (
20
06
) 4
89
not
ann.
4 m
in. a
nn.
�E
nhan
cem
ent
of t
he
deg
ree
of
order
/cri
stal
lini
tyof
P3
HT
�O
rder
/dem
ixin
gfa
vour
p an
d n
pe
rcol
atio
npa
ths
form
atio
n
NIS
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27
Ann
ealing
120
°C
Mic
rosc
opia
TE
M1
.5 µ
m
X. Y
ang
etal
s. N
anoL
ette
rs5
, 5
79 (
200
5)
P3H
T:P
CB
M, 1:
1
order
↔ph
ase
segr
egat
ion
Mic
haile
tchi
, Adv.
Fun
ct. M
ater
. 2006
, 16
, 69
9
Spa
ce C
har
ge L
imit
ed m
obilit
ies
upon
ann
ealing
, hol
e m
obilit
y in
th
e ble
nd r
each
es P
3H
T p
rist
. va
lues
! NIS
Col
loqu
ium
–T
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o2
3 G
iugn
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008
28
D:A
sel
f-or
gani
sati
on?
L. S
chm
idt-
Men
deet
als.
Sci
ence
(2001)
293
, 111
9
DA
:4
0:6
0
Dou
ble
cable
S
(CH
2) 5
O
O
O
O
C1
2H
25
S
C1
0H
21
XY
n
M. C
atel
lani
et
als.
, J
. Mat
er. C
hem
. 14
, 6
7 (
20
04);
S. L
uzza
ti e
tal
s. P
roc.
SPI
E V
ol. 5215
, p.
41,
Org
anic
Phot
ovol
taic
sIV
(20
04
)
NIS
Col
loqu
ium
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iugn
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008
29
Ano
ther
exam
ple
of s
elf
orga
nisa
tion
Inte
rest
ing
mor
phol
ogie
s but
ver
y lo
w e
ffic
ienc
ies
Cur
rent
ly D
:A b
lend
s le
ads
to b
ette
r pe
rfor
man
ces
NIS
Col
loqu
ium
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orin
o2
3 G
iugn
o2
008
Thel
laka
tgr
oup,
F
reib
urg
Uni
v.
30
Key
prop
erti
esof
BH
J a
ctiv
em
ater
ials
η=
= FF
P el.
out
P inc
.
Isc
Voc
P inc.
•so
lar
spec
trum
har
vest
ing
�H
OM
O-L
UM
O lev
els
∝ ∝∝∝Voc
DA
�m
orph
olog
yan
d c
har
getr
ansp
ort
NIS
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31
New P
New P
(bet
ter
than
P3H
T)::
•• Low
ering
Low
ering
band
gap
band
gap
•• Inc
reasing
Inc
reasing
oxid
ation
oxid
ation
pote
ntial
pote
ntial
Voc
Voc
∝ ∝∝∝∝ ∝∝∝Lum
oLum
o--Hom
oHom
o
P3HT
P3HT
low
erin
gban
d g
ap o
ften
dec
reas
esox
. pot
enti
al!
Des
ign
of n
ew p
olym
ers
P:PC
BM
bul
k het
eroj
unct
ion
DA
∝ ∝∝∝Voc
NIS
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loqu
ium
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008
32
*cha
rge
phot
ogen
erat
ion
and
tran
spor
tsi
mila
rto
P3H
T:P
CB
M
Idea
l don
or p
olym
ers
for
P:PC
BM
BH
J
conv
. eff
.
M. Scharberetals, Adv. Mater18, 789 (2006)
Don
or p
olymer
featu
res
�HOM
O
~ 5
.7-
5.8
eV
�Eg
~ 1
.8-2 e
V
�go
od c
harg
e m
obility
�go
od b
lend
mor
pholog
y
Poly
mer
:pcb
mso
lar
cells
up
to
10
-12
% e
ffPo
lym
er:p
cbm
sola
r ce
lls
up t
o 1
0-1
2%
eff
NIS
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ium
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orin
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008
33
conc
lusi
ons
“pla
stic
”so
lar
cells
: lo
w c
ost
and u
ncon
vent
iona
l ap
plic
atio
ns
effi
cien
cies
hav
e dra
stic
ally
im
prov
ed in
the
last
thre
e ye
ars,
rea
chin
g 5
%, a
thre
shol
d t
hat
ope
ns u
p to
the
mar
ket
the
des
ign
of t
he
orga
nic
phot
oact
ive
mat
eria
l has
a
key
role
for
the
effi
cien
cies
so
far
atta
ined
, an
d f
or
futu
re p
rogr
esse
s
in t
he
near
fut
ure
10-1
2 %
eff
are
expe
cted
for
sin
gle
cells
and
15
% f
or t
andem
cel
ls
NIS
Col
loqu
ium
–T
orin
o2
3 G
iugn
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008
34
Tec
hno
logi
calis
sues
Roo
ftop
tes
ting
of
BH
J s
olar
cel
ls a
t K
ON
AR
KA
Flexib
le O
rganic
P3HT:P
CBM
Bulk-
Hete
roju
nction
Mod
ules
with m
ore t
han
1 Y
ear
Out
doo
r Lifetime
NIS
Col
loqu
ium
–T
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35
Asp
etti
tec
nolo
gici
: in
caps
ulam
ento
O
PV f
less
ibili
oLE
Ds
celle
sol
ari
G.D
ennl
eret
al.,
J. M
ater
Res
. 20
, 3
32
4, (2
00
5);
Req
uisi
ti d
i im
perm
eabilit
àal
l’oss
igen
o e
all’a
cqua
per
l’e
lett
roni
ca o
rgan
ica
Cel
le s
olar
i in
caps
ulat
e
Sta
bili
tàal
l’ari
a m
dm
oppv
:pcb
m
Inca
psul
amen
to
con
film
di PE
T
*In
caps
ulam
ento
co
n fi
lm d
i po
liet
ilen
naft
alen
etr
atta
to c
on
bar
rier
a
*
bar
rier
a: m
ulti
laye
ror
g/in
org
P. M
adak
asir
aet
als,
Syn
th. M
etal
s15
53
32
(2
00
5)
NIS
Col
loqu
ium
–T
orin
o2
3 G
iugn
o2
008
36
Gra
zie p
er
Gra
zie p
er
ll ’’ att
enz
ione
att
enz
ione
NIS
Col
loqu
ium
–T
orin
o2
3 G
iugn
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008
ww
w.h
ertz
-lan
gber
g.co
m