Bernard Kippelen Seminar

Seminar
Series, UCSB, Santa Barbara, CA, January 21, 2015
Organic Semiconductors
for Energy Efficiency
Bernard Kippelen

Joseph M. Pe+t Professor

School of Electrical and Computer Engineering
Director, Center for Organic Photonics and Electronics

EFRC
Acknowledgments
Canek
Fuentes
Hernandez
Amir
Dindar
Talha
Khan
Vladimir
Kolesov
Michael Gaj
Albert Ernst
Sangmoo
Choi
Cheng-Yin
Wang
S.R. Marder (GT)

N. R. Armstrong (UA)
Minseong
Yun
Keith
Knauer
Ehsan
Najafabadi
Yinhua
Zhou
J-L Bredas (KAUST)

S. Graham (GT)
A. Kahn, Princeton
J. Youngblood, Purdue
Mathieu
Fenoll
James
Hsu
Do Kyung
Hwang
R. Moon, Purdue
Jaewon
Shim
Global macro trends: the

zetta era
Increasing energy
demand: 16 TW
in 2007 (0.5 ZJ),
28 TW by 2050
(0.9 ZJ)
Increasing popula.on:
7.1 Billion today, 9 Billion
by 2050
Food and
water
supplies?
Healthcare
and security?
25% of the world

popula_on lacks
electricity
Impact to the
environment?
Giga (9), tera (12), peta (15), exa (18), zeaa (21)
Innovation
Disruptive technologies
High-end market
needs
Low-end market
needs
Adapted from The Innovators dilemma, Clayton Christensen

5
Organic semiconductors
Semiconductor thin
lm
The vision: flexible printed

electronics
Georgia Tech
Georgia Tech
Low cost, large area, and lower capital

investment per manufacturing line.
Konarka
Intelligence with portable power

everywhere.
7
Outline

q Organic light-emijng diodes

q Organic eld-eect transistors

q Organic photovoltaics

The dawn of the OLED era
Samsung
Philips
Organic light-emitting diode
Metal cathode
Electron transport
Light emission
Hole transport
ITO anode
Tang and VanSlyke Appl. Phys. Lea. 51, 913 (1987)

10
From fluorescence to
phosphorescence
Frster
Fluorescence
Dexter
S1
Metal cathode
Electron transport
Light emission
S1
T1
T1
Hole transport
ITO anode
S0
Host
Guest
S0
Baldo et al., Nature 395, 151 (1998)

Tang et al. Appl. Phys. Lea. 51, 913 (1987)
Control energies of singlet and triplet states of host to allow for ecient energy
transfer to the guest.
Ensure balanced hole and electron transport.
11
Trends in device architecture

Conven_onal OLED architecture: emission through boaom transparent substrate
limits pixel aperture ra_o.

ITO used as transparent boaom electrode and its high work-func_on denes the
anode.
NMOS transistors for
AMOLED displays:
D
IDS
G
S
Need for boaom cathode (Al), top-

emijng OLEDs

Anode
Al cathode
Substrate
12
Green bottom-cathode, topemitting OLED

N
Ir
N
Ehsan
Najafabadi
-NPD (120 nm)

Au (20 nm)
MoO3 (15 nm)
Keith
Knauer
Ir(ppy)3
Green emitting guest
CBP (35 nm)

CBP:Ir(ppy)3 6% (20 nm)
CBP
TpPyPB (40 nm)
LiF (2.5 nm)

Al (40 nm)
TpPyPB
PEDOT:PSS (40 nm)

Glass/plas_c
E. Najafabadi, B. Kippelen, et al. Appl. Phys. Let.

101,023304 Jul. (2012)

K.E. Knauer, Appl. Phys. Lea. 101, 103304 Sep. (2012)
Out-coupling layer: Q. Huang , K. Leo et al. J. Appl. Phys. 100, 064507 (2006)
13
35
5
10
30
Luminance (cd/m )
10
KAK-II-38F
10
25
20
15
10
10
10
Voltage (V)
Voltage (V)
Luminance
(cd/m2)
Voltage (V)
EQE* (%)
Current Density
(mA/cm2)
Current Efficacy (cd/A)
10
3.6
30.1
1.5 x 10-2
109.7
100
4.2
29.1
1.4 x 10-1
106.1
1,000
5.0
25.4
1.4
92.5
10,000
6.2
20.3
14.2
74.1
100,000
8.8
9.7
280.1
37.4
(*) EQE measured assuming Lamber_an emission
10
KAK-II-38F
EQE (%)
Current Density (mA/cm )
10
3
10
2
10
1
10
0
10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
-2
Inverted top-emitting OLEDs on

glass
14
Inverted multi-junction
OLEDs
Light extrac_on
Transparent anode
Light extrac_on
Hole transport 2
Transparent anode
Hole transport
Light emission
Light emission 2
Electron transport
Al cathode
Single junc_on:
L (cd/m2) = f (V1 , J ) (mA/cm2)
Max. eciency: 100%
Electron transport 2
Charge genera_on
Hole transport 1
Light emission 1
Al cathode
Double junc_on:
L (cd/m2) = 2 f (V2 , J ) (mA/cm2)
Max. eciency: 200%

Lower current for same luminance can lead to longer life_me
15
Stacked double-junction
inverted OLED
TAPC (35 nm)

TpPyPB (40 nm)
LiF (2.5 nm)
Al (50 nm)
PEDOT:PSS (40 nm)
Glass
Luminance (cd/m )
HAT-CN (10 nm)
10
2 Unit Stacked OLED

Single OLED
10
10
10
KAK-II-99D,F
10
-2
8 10 12 14 16 18
30
28
26
24
22
20
18
16
14
12
10
8
6
4
2
0
EQE (%)
+
-
Au (20 nm)
MoO3 (15 nm)
TAPC (35 nm)
TpPyPB (40 nm)
LiF (1.0 nm)
Al (2.5 nm)
Voltage (V)
Charge genera_on layer (HATCN:TAPC) : T. Chiba , J. Kido, and coworkers, Org.

Electron. 12, 710 (2011)
16
Light extrac_on
Transparent anode
Hole transport 2
Light emission 2
Charge genera_on
Hole transport 1
Light emission 1
Al cathode
Efficacy with light outcoupling

layer
220
200
180
160
140
120
100
80
60
40
20
0 1
10
Single-unit OLED
Double-unit OLED
Double-unit OLED
with outcoupling
10
10
10
10
Luminance (cd/m )
q 200 cd/A @ 1,000 cd/m2

q 100 cd/A @ 100,000 cd/m2
KAK-II-99D3
KAK-II-99F5
KAK-II-112G4
K. A. Knauer et al., Org. Electron. 14, 2418 Jun. (2013).
17
Thermally activated delayed

fluorescence (TADF)
All-organic compounds that do not contain precious

metals
Uoyama, H., Goushi, K., Shizu, K., Nomura, H., Adachi, C. Nature. 492, 234 (2012).
Nakanotani, H., Masui, K., Nishide, J., Shibata, T., Adachi, C., ScienTc Reports. 4, 2127 (2013).
18
TADF device structure

Adachi TADF
emiaer
(e)
TPBi
(d)
Host
19
10
10
25
4
10
10
1
10
20
L (cd/m )
10 0
10 -1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
-2
15
10
10
2
10
MPG_III_70C
3 Devices Shown
5
MPG_III_70C
3 Devices Shown
-2
EQE (%)
Current Density (mA/cm2)
TADF device performance
Voltage (V)
0
8
Voltage (V)
Device
Luminance
(cd/m2)
Volt (V)
EQE (%)
cd/A
Lm/W
mA/cm2
65nm TPBi

22
3.2
23.1
70.1
68.8
0.03
177
3.6
22.2
67.4
58.9
0.26
948
4.2
20.9
63.3
47.4
1.50
10252
6.2
13.1
39.9
20.2
25.7
M. Gaj, B. Kippelen et al. Org. Electron. 16, 109-112 Jan. (2015)
20
80
80
60
60
40
40
20
20
MPG_III_70C
3 Devices Shown
10
10
Luminance (cd/m )
10
Power Efficacy (Lm/W)
TADF device roll-off
M. Gaj, B. Kippelen et al. Org. Electron. 16, 109-112 Jan. (2015)
21
Device platform #2




22
Atomic layer deposition for

OFETs
Xiaohong
Zhang
OFETs with ALD gate dielectric: Zhang et al. Org. Electron. 8 718 (2007)
Zhang, Kippelen, et al. Appl. Phys. LeT. 94, 043312, Jan. (2009)
23
OFETs with bilayer gate

Bi-layer gate
dielectric
Al
-7
IDS (A)
10
Glass
CH3
CH3
O
C
F2
Si
TIPS-Pentacene
CF2
CF CF
PTAA
2.5
W/L = 2550 m/180 m

VDS = - 8 V
2.0
VTH= - 3.6 V ,
2
= 1.11 cm /Vs
1.5
-8
10
1.0
-9
10
IG
0.5
-10
F2C
H3 C
-6
10
Al2O3 (50 nm)

CYTOP (40 nm)
TIPS-pentacene + PTAA

Au
Au PFBT
PVP
Si
-5
10
10
n
CF2
CYTOP
(Asahi glass)
-11
10
-2
-4
-6
0.0
-8
VGS (V)
Low-voltage opera.on
and high mobility
D.K. Hwang, B. Kippelen, et al. Advanced Materials, 23, 1293 Jan. (2011)
24
IDS 1/2 ( A)1/2
Do Kyung
Hwang
Stability or organic
semiconductor devices
20,000 cycles
CYTOP (40 nm)/Al2O3 (50 nm)
-5
10
W/L = 2550 m/180 m

-6 VDS = - 8 V
10 Plot every 2000th interval
Al
Glass
-7
IDS (A)
Al2O3 (50 nm)

CYTOP (40 nm)

Au
Au PFBT
PVP
10
-5
10
-6
10
-7
10
-8
10
-9
10
-10
10
-11
10
-8
10
-9
10
-10
10
D.K. Hwang, B. Kippelen, et al.
Advanced Materials, 23, 1293 Jan.
(2011)
-11
10
Plot every
th
100 interval
-2
-4
-2
VGS (V)
-4
-6
-6
-8
-8
25
Environmental tests
Al
Al2O3 (50 nm)
CYTOP (40 nm)

Au
Au PFBT
PVP
Glass
= 1.48 cm2/Vs
D.K. Hwang, B. Kippelen, et al. Advanced Materials, 23, 1293 Jan. (2011)
26
Environmental test results

Pristine
Oxygen
Air for 11plasma
months
Air for 11plasma
months
Immersion
in water
Oxygen
-5
10
-7
1/2
10
( A)
VDS = - 8 V
-8
10
-9
10
IDS
IDS (A)
1/2
-6
10
-10
10
OFET: DK-I-79
-2
-4
VGS (V)
-6
0
-8
Exposure sequence
W/L
(cm2/Vs)
VTH (V)
Pris.ne
2550m/180 m
1.48
- 4.2
Normal Air for 11 months
2550m/180 m
1.34
- 2.9
Oxygen plasma for 5 min

Immersion in water for 1 h
2550m/180 m
2550m/180 m
1.28
1.25
- 2.7
- 2.6
D.K. Hwang, B. Kippelen et al. ACS APPLIED MATERIALS & INTERFACES 6, 3378-3386 (2014)
27
Ink-jet printed OFETs
Al
Al2O3 (50 nm)
CYTOP (45 nm)
NDI-BTTZ-NDI

pAg
pAg
PES
IDS (A)
10
-8
1.0
1/2
10
1/2
1.5
-7
( A)
-6
10
2.0
W/L = 2000 m/180 m

VDS = 10 V
-9
10
0.5
-10
10
IDS
Ac_vInk N2200
VTH= 1.8 V ,
2
Marder group
10
D.K. Hwang et al. Adv. Mater. 24, 4445-4450 (2012)
= 0.17 cm /Vs
-11
-2
VGS (V)
0.0
10
public\shared\OFET\Do Kyung\DK-II-19_Reddy\TR\Printed TR\Ag and di-CB PES
28
Water-stable OFET for biological

sensing
Stable operation under water
MY2012#1P60-A_R204
0.8
0.3
0.2
-9
10
in air
under DI water
-1
VGS (V)
-2
R:\Public\Shared\OFET\Minseong\MY2012\#1P60-A\R204W2550L180\2. After 93 days
0.1
0.0
-3
1/2
500
1000
1500
2000
2500
3000
500
1000
1500
2000
2500
3000
-0.20
-0.15
-0.10
Cysteine ( L) DI water ( L)
0.4
-8
10
( A)
0.5
1/2
-IDS (A)
0.6
(-IDS)
-7
-0.25
0.7
W/L= 2550 m/180 m

VDS= -2 V
IDS ( A)
Ag gate
10
Repeatable sensor response to cysteine
0
2
0
0
Time (s)
M. Yun, B. Kippelen, et al. ACS APPLIED MATERIALS &
INTERFACES 6 (3), 1616-1622 (2014)
29
Device platforms




Copyright: Virginie Drujon-Kippelen
30
Organic photovoltaics
Hole-collec_ng
electrode
Absorber
e
Electron-collec_ng
electrode
M. F. Toney, A. Salleo and co-workers, Chem. Rev. 2012, 112 (10), 5488.
31
Energy level diagram

Energy (eV)
a) In the dark
b) Under illumina_on
q
WH
EF
WL
LUMOA
Fn
WH
WL
Fp
HOMOD
Electrode / ABSORBER / Electrode
Under illumina_on: photocurrent and photovoltage
32
Challenges in organic
photovoltaics
qSemiconductor devices (solar cells) require electrodes, one of which

should have low work func.on.
qDierence in work func_on between contacts is an upper limit for open-
circuit voltage in solar cells: need for large dierence in work func.on.

qLow-work func_on metals (e.g. Ca) are highly reac_ve in air, metal-
oxides dicult to process.
33
Polymeric surface modifiers

Low WF
High WF
PVP
ITO
ITO
Polyvinylpyrrolidone (PVP)
Work func_on measured by Kelvin probe (Besocke Delta Phi) and
averaged over three loca_ons.
Jaewon
Shim
Samples
Work func.on (eV)
ITO
4.62 0.06
ITO/PVP (1 nm)
4.20 0.06
34
UPS characterization
Collabora_on with Kahn Group at Princeton
!
Shiy of the photoemission onset indica_ve
of a downward shiy of the vacuum level
created by a surface dipole.
ITO: WF = 4.4 eV
ITO/ PVP: WF = 3.6 eV

J. Shim, A. Kahn, B. Kippelen et al. Appl. Phys. Lea. 101, 073303 Aug. (2012)
35
Polymeric surface modifiers:

optimization
PH1000
PH1000 + PEIE
Yinhua
Zhou
N
x
N
HO
N
H
Intensity (A.U.)
OH
OH
ITO
ITO + PEIE
Au
Au + PEIE
OH
PEIE
H2N
NH2
N
a
-18
-17
-16
E w.r.t. Fermi level (eV)
NH
N
H
b
d
N
H2N
PEI
NH2
Modeling: J.L. Bredas

group on ethylamine
UPS
measurements:
Kahn group
Y. Zhou, S.R. Marder, J.L. Bredas, S. Graham, A. Kahn, B. Kippelen et al. Science, 336,
327 April 20 (2012).
36
ITO/PEIE
4.8
4.5
Work function (eV)
Work function (eV)
Thermal and environmental

stability
ITO
4.2
3.9
ITO/PEIE
4.8
ITO
4.5
4.2
3.9
3.6
3.6
0
100
200
300
O
Temperature ( C)
400
10
100
1000
Time exposed in air (h)
37
Validation in solar cells

Ag (150 nm)
PBDTTT-C:PC60BM
Polymeric surface modier
ITO
Glass
Current Density (mA/cm
MoO3(10 nm)
40
30
20
10
J (A/cm 2)
50
1m
1
1n
-1
0
V (V)
-10
Dark
Light
-20
-1.0
-0.5
0.0
0.5
1.0
Voltage (V)
Substrate name
Active layer
VOC
(mV)
JWS-III-124K
PBDTTT-C:PC60BM
6771
JSC
(mA
cm-2)
FF
(%)
16.10.4
0.610.01
6.6 0.2
38
First completely plastic solar cell
39
Completely plastic solar cell

ICBA
P3HT:ICBA
PEDOT-blend
P3HT
PEI
PEDOT:PSS
1.0
Normalized PCE
II
III
IV
0.8
VI
I: Newly fabricated
II: Fixed on a roll with R = 5.4 mm
III: Fixed on a roll with R = 3.5 mm
IV: Bended 400 _mes with R = 6.3 mm
V: Bended 400 _mes with R = 5.4 mm
VI: Bended 400 _mes with R = 3.9 mm
0.6
0.4
0.2
0.0
SO3
Current Density (mA/cm )
PES
J (A/cm )
PH1000
6
4
1m
1
1n
2
0
-2
-4
-1
0 1
V (V)
VOC : 0.80 0.02 V

JSC : 7.1 0.3 mA/cm2
FF : 0.52 0.02
PCE : 3.0 0.2%
-6
All-polymeric
-8
-0.2
0.0
0.2
0.4
0.6
0.8
Voltage (V)
Continuous bending
Y. Zhou, S.R. Marder, J.L. Bredas, S. Graham, A. Kahn, B. Kippelen et al. Science, 336,
327 April 20 (2012).
40
Modeling of organic solar cells

FF, JSC and VOC are not independent parameters
Device are not perfect diodes
RS
J
Jph
J0 ,
n
RP
1
J=
1+ RS /RP
V JR A
V
S
J 0 exp
1 J ph
RP A
nVT
41
Current-voltage
characteristic
Low shunt resistance device
Current (mA/cm )
20
15
J (A/cm2)
25
10m
10
10n
10p
10
-1
0
1
V (V)
0
-5
-10
T K- V-1 35 C#1
-1.0
-0.5
0.0
0.5
1.0
Voltage (V)
ITO/PEIE/P3HT:ICBA/MoO3/Ag
42
Experiment vs. theory

Shockley diode
predicts:
VOC
J SC
nkT
=
ln(
+ 1)
e
J0
43
High shunt resistance

device
High shunt resistance device
Current (mA/cm )
20
15
10
J (A/cm2)
25
10m
10
10n
10p
-1
0
1
V (V)
0
-5
-10
T K- V-1 35 C#4
-15
-1.0
-0.5
0.0
0.5
1.0
Voltage (V)
44

(revisited)
45

(revisited)
0.9
0.8
0.7
High shunt resistance

Low shunt resistance
Voc (V)
0.6
0.5
VOC
0.4
J SC
nkT
=
ln(
+ 1)
e
J0
0.3
0.2
0.1
0.0
High shu nt : T K-V- 135 C#4

Low shu nt: T K-V- 135 C#1
-0.1
-3
-2
-1
0
10 10 10
10
10
10
10
10
10
Jsc (A/cm )
46
Influence of shunt
resistance
a)
c)
b)
47
Modeling with equivalent

circuit
48
Additive transfer lamination

PES/PEDOT:PSS/PEI/P3HT:ICBA-L/PEDOT:PSS-L
PH1000-L
P3HT:ICBA-L
PEI
PH1000
PES
Nomenclature: sux -L means layer has been transfer laminated

Collabora_on with A. Kahn and L. Loo
49
J-V characteristics
Current (mA/cm )
10m
J (A/cm )
10
10
10n
10p
-1
0
V (V)
0
YHZ-III-135D#2,3
-2
-4
-6
-1.0
-0.5
0.0
0.5
1.0
Voltage (V)
50
Light-intensity dependence
0.9
dark
ISC (A):
4.5e-10
8.4e-10
2.36e-9
5.68e-9
2.75e-8
5.67e-8
1.07e-7
3.0e-7
5.1e-7
6.74e-7
2.08e-6
8.7e-6
1.85e-5
5.8e-5
2.23e-4
0.1
0.01
1E-3
1E-4
1E-5
1E-6
1E-7
1E-8
-1.0
-0.5
0.0
0.5
0.8
0.7
VOC (V)
Current density (mA/cm )
10
0.6
0.5
room light
0.4
0.3
YHZ-III-135N#2
0.2
1E-10 1E-9 1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0.01
1.0
ISC (A)
Voltage (V)
Y. Zhou et al. J. Mater. Chem. A, 2, 3492 Feb. (2014)
VOC =
I
nkT
ln( L + 1)
e
I0
n = 1.82
J0 = 6.2 10-11 A/cm2
51
Sustainable and green?
Need earth abundant materials and renewable materials

Develop green manufacturing and sustainable products that can be recycled
Move from petroleum chemistry to naturally-derived materials
52
Forest nanotechnology
M. Postek et al. Meas. Sci. Technol. 22, 024005, 2011

53
Recyclable solar cells
Y. Zhou et al., Sci. Rep. 3, 1536 Mar (2013).
54
Recycling of organic solar

cells
55
The path forward
Low
cost
Long
life_me
High
eciency
Plenty of room for new science, engineering and
innova_on
56
57

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Seminar

Series, UCSB, Santa Barbara, CA, January 21, 2015

Joseph M. Pe+t Professor

S.R. Marder (GT)

J-L Bredas (KAUST)

Global macro trends: the

25% of the world

Adapted from The Innovators dilemma, Clayton Christensen

The vision: flexible printed

Low cost, large area, and lower capital

Intelligence with portable power

q Organic light-emijng diodes

The dawn of the OLED era

Organic light-emitting diode

Tang and VanSlyke Appl. Phys. Lea. 51, 913 (1987)

Baldo et al., Nature 395, 151 (1998)

Trends in device architecture

Need for boaom cathode (Al), top-

Green bottom-cathode, topemitting OLED

-NPD (120 nm)

CBP (35 nm)

TpPyPB (40 nm)

LiF (2.5 nm)

PEDOT:PSS (40 nm)

E. Najafabadi, B. Kippelen, et al. Appl. Phys. Let.

Current Efficacy (cd/A)

(*) EQE measured assuming Lamber_an emission

Current Density (mA/cm )

Inverted top-emitting OLEDs on

Lower current for same luminance can lead to longer life_me

TAPC (35 nm)

HAT-CN (10 nm)

2 Unit Stacked OLED

Charge genera_on layer (HATCN:TAPC) : T. Chiba , J. Kido, and coworkers, Org.

Current Efficacy (cd/A)

Efficacy with light outcoupling

q 200 cd/A @ 1,000 cd/m2

K. A. Knauer et al., Org. Electron. 14, 2418 Jun. (2013).

Thermally activated delayed

All-organic compounds that do not contain precious

TADF device structure

Current Density (mA/cm2)

TADF device performance

M. Gaj, B. Kippelen et al. Org. Electron. 16, 109-112 Jan. (2015)

Power Efficacy (Lm/W)

Current Efficacy (cd/A)

TADF device roll-off

M. Gaj, B. Kippelen et al. Org. Electron. 16, 109-112 Jan. (2015)

q Organic light-emijng diodes

Atomic layer deposition for

OFETs with bilayer gate

W/L = 2550 m/180 m

Al2O3 (50 nm)

IDS 1/2 ( A)1/2

CYTOP (40 nm)/Al2O3 (50 nm)

W/L = 2550 m/180 m

Al2O3 (50 nm)

Environmental test results

Normal Air for 11 months

Oxygen plasma for 5 min

Ink-jet printed OFETs

W/L = 2000 m/180 m

D.K. Hwang et al. Adv. Mater. 24, 4445-4450 (2012)

public\shared\OFET\Do Kyung\DK-II-19_Reddy\TR\Printed TR\Ag and di-CB PES