Recent Advances in Organic Electronics

IEE/CEEM Seminar October 21, 2009

UCSB

Wesley Walker
Toan Pho
Dr. Rajeev Kumar
Dr. Fulvio Brunetti
Dr. Changduk Yang

Prof. Yang Yang

Profs. Alan Heeger and Quyen Nguyen

Support MRL CPOS

Air Force MC-CAM

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 Organic Semiconductor Devices

Light Emitting Diodes Field Effect Transistors PhotoVoltaic Cells

 Cell phones  Radio frequency ID tag  Low-power

consumption or
 Flat-panel TV  Smart cards
disposable devices
 Lighting  Organic active matrix
displays

.; Yu, G.; Liu, Y.; Zhu, D. J. Phys. Chem. B. 2007, 14083.

Y.; Kageyama, H. Chem. Rev. 2007, 953.
ic Electronic (Molecular) Mater

Design Molecule

Ensemble Molecules

PropertiesSolid State

Metals?Yes! Semiconductors?Yes!
Yes!
Superconductors?
Ferromagnets, Ferroelectrics, NLO, etc
 White Light Organic Electroluminescence

, Y.; Duong, H. M.; Wudl, F. Appl. Phys. Lett., 2004, 85(16), 3357
Gong, X.; Ma, W.; Ostrowski, J.C.; Bazan, G.C.; Moses, D.; Heeger, A.J. Adv. Mater. 2004, 16, 615
 Photovoltaic (Organic) Devices

Efficient Tandem Polymer Solar Cells Fabricated by All-Solution

Processing Kim, J.Y.; Lee, K.; Coates, N.E.; Moses, D.; Nguyen, T.-
Q.; Dante, M.; Heeger, A.J. Science, 2007, 317, 222-225

“Power-conversion efficiencies of more than 6% were

achieved at illuminations of 200 milliwatts per square
centimeter”
 Organic Electronics: Organic
Semiconductors

Polymeric Light Emitting Diodes (PLEDs)

Polymeric Photovoltaics (P-PVs)

Polymeric Electrochromics

Polymeric Field Effect Transistors (PFETs, PTFTs)

Organic Light Emitting Diodes (OLEDs)

Organic Photovoltaics (O-PVs)
Organic Field Effect Transistors (OFETs, OTFTs)

Organic Memory Devices (OMDs)

Organic Semiconductors: Key Parameters

Semiconductor gap, Eg [E(π- π*)]

Relative HOMO vis a vis electrode material

Relative LUMO vis a vis electrode material

Nature of the charge-carrier (h(+) or e(-))

Charge-carrier mobility (μ)

Processing and morphology

 Organic Electronics: Organic
Semiconductors

Polymeric Light Emitting Diodes (PLEDs)

Polymeric Photovoltaics (P-PVs)

Polymeric Electrochromics

Polymeric Field Effect Transistors (PFETs, PTFTs)

Organic Light Emitting Diodes (OLEDs)

Organic Photovoltaics (O-PVs)
Organic Field Effect Transistors (OFETs, OTFTs)

Organic Memory Devices (OMDs)

Organic Semiconductors: Challenge for
OLEDs

Stable, high-efficiency blue-light emission

High-efficiency white light production

 A Blue Emitting Fluoranthene

N N
O

N N

R R R R R R
21,750 cd/m2
N N
6.1 Cd/A 14,000 cd/m2
Si

N N 1.53 Cd/A

Wu, C-C; Lin, Y-T; Wong, K-T; Chen, R-T;

Chan, L-H; Lee, R-H; Hsieh, C-F; Yeh, H-C; Chen, Chien, Y-Y Adv. Mater. 2004, 16, 61-65
C-T J. Am. Chem. Soc. 2002, 124, 6469-6480
O O O

O
KOH Xylenes
EtOH /  200 ºC

TPF
C.; Tseng, R.J.; Marchioni, F.; Yang, Y.; Wudl, F. Adv. Mater., 2006, 18(3),
Photoluminescence of TPF

Absorption
Fluorescence
PMMA
Fuorescence 77K
Phosphorescence 77K

Filippo Marchioni
Electronic Process in Fluorescence and OLEDs

+h -h

-h
-e- +e-
 A Cartoon View of OLEDs at Work

e-
e-
Metal Anode

Emissive Layer

Transparent
Cathode

h+ h
+ h
h
OLED Data (Ricky Tseng)

Ca /Al
BCP 30nm

TPF 20nm

CBP 15nm 5910 cd/m2

NPB 15nm

ITO/PEDOT
 Acronyms

N N

NPB

N N
N N

BCP
CBP
 OLED Data (Ricky Tseng)

A Maximum brightness of 5910 cd/m2 can be observed and

maximum luminescence efficiency of 3 cd/A can be achieved
at 3 mA/cm2 and 100 cd/m2.

Chiechi, R.C.; Tseng, R.J.; Marchioni, F.; Yang, Y.; Wudl, F. Adv.
Mater., 2006, 18(3), 325-328).
Organic Semiconductors: Challenge for
OLEDs

Stable, high-efficiency blue-light emission

High-efficiency white light production

The Lower Linear Oligoacenes
 The Twistacenes

Ph Ph
O
+ O O
O
Ph Ph

TMS OTf

Ph Ph Ph
TfO TMS

O
TBAF
Ph CH2Cl2 Ph Ph
22%
TBH

A twisted heptacene
Crystal Structure of a Truly Contorted
Molecule
Photoemission Spectrum

= 15%
in toluene
Photoluminescence of White
Photoluminescence PF Doped
Lightwith
TBH

90% blue PF: 10% C66H38

1.2 93% blue PF: 7% C66H38
Normalized PL intensity(a.u.) 95% blue PF: 5% C66H38
1.0 99% blue PF: 1% C66H38
99.5% blue PF: .5% C66H38

0.8

0.6

0.4

0.2

0.0
400 450 500 550 600 650 700
Wavelength(nm)
 OLED: IV Curve
ITO/PEDOT/BP 99%:C66H381% 1450rpm/15A LiF/300A Ca/800A Al
3 4
10 3.0
10
2
10 2.5

2.0 3
10
1 cd/A 10
Current Density(mA/cm )

1.5
2

0 1.0
10

Brightness(cd/m )
0.5 2
-1 10
10 0.0
0 10 20 30 40 50

-2 Current(mA
10 1
10
-3
10
-4
10

2
0
CIE:(x=0.320;y=0.362)
10
-5
10
-6 -1
10 10
-6 -4 -2 0 2 4 6 8 10 12 14
Voltage(V)
OLED: IV Curve

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Electroluminescence of PF Doped with TBH

EL Normalized Intensity(a.u.)
90% blue PF: 10% C66H38
1.4
93% blue PF: 7% C66H38
95% blue PF: 5% C66H38
1.2 99% blue PF: 1% C66H38
99.5% blue PF: .5% C66H38
1.0

0.8

0.6

0.4

0.2

0.0
400 450 500 550 600 650 700
Wavelength(nm)
 Electroluminescent Device Based on PF-TBH:
by Qianfei (Faye) Xu in The Yang Yang Group
Ph Ph

Ph Ph
TBH

CIE x = 0.32, y = 0.36!!

Yang, Y.; Duong, H. M.; Wudl, F. Appl. Phys. Lett., 2004, 85(16),
International Color Standard

CIE 1931 xy diagram

 Organic Electronics: Organic
Semiconductors

Polymeric Light Emitting Diodes (PLEDs)

Polymeric Photovoltaics (P-PVs)

Polymeric Electrochromics

Polymeric Field Effect Transistors (PFETs, PTFTs)

Organic Light Emitting Diodes (OLEDs)

Organic Photovoltaics (O-PVs)
Organic Field Effect Transistors (OFETs, OTFTs)

Organic Memory Devices (OMDs)

 “We face a true planetary emergency. The
climate crisis is not a political issue, it is a moral
and spiritual challenge to all of humanity.”

-Al Gore, 2008 Nobel Peace Prize winner

A P-LED and P-PV are the Reverse of
Each Other

Charge
O
(electricity)
h

n
R O
Diode
Diode
(CH2)3CO2Me
C6H5 O

+
n
h O
Charge PCBM
(electricity) R
Electronic Process in OLEDs and OPVs

Electricity

+h
+e-

-e-
Fullerene-PPV Plastic
Solar Cell
(N.S. Saiciftci)

Electron
Transfer

PCBM

MDMO-PPV

Courtesy of Prof. Saricif

osed Interaction between Polymer and Fullerene Deri
(N.S.Sariciftci)

Courtesy of Prof. Saricift

Organic Semiconductors: Key Challenges for
Conjugated Polymers in Photovoltaics

High charge-carrier mobility ()

Matching absorption to the solar spectrum (Eg 0.6 - 3 eV)

High positive charge-carrier mobility,  (p-type semiconductor)

Processing and morphology

The Most Popular Conjugated Polymers
H
N
(CH)x n
PA PANI

O O
n

PPP S n S n
PITN PEDOT
Y
X
Z

X
X = S, NH, NR; Y = H, R, Ph, etc
PT, PPy, etc Y
PPVs

X Y
PFs
 Possible P3HT Stereochemistries

R R

S S
S S

R R

P3HT
R R

S S
S S

R R

H-T-rr-P3HT

R R

S S
S S

R R

H-H-T-T-rr-P3HT

R = hexyl (C6H13)
 Modern Protagonists

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David Mühlbacher, Markus Scharber, Mauro Morana, Zhengguo Zhu, David Waller,
Russel Gaudiana, and Christoph Brabec Adv. Mater. 2006, 18, 2884–2889
 Photovoltaics: Key Parameters

 = Power Conversion Efficiency (PCE)

 = Jsc · Voc · FF
Jsc = Short circuit current
Voc = Open circuit voltage

FF = f(Jsc · Voc)
 Typical Experimental Result

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David Mühlbacher, Markus Scharber, Mauro Morana, Zhengguo Zhu, David Waller,
Russel Gaudiana, and Christoph Brabec Adv. Mater. 2006, 18, 2884–2889
 Fundamental Processes

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David Mühlbacher, Markus Scharber, Mauro Morana, Zhengguo Zhu, David Waller,
Russel Gaudiana, and Christoph Brabec Adv. Mater. 2006, 18, 2884–2889
 Parameters That Affect rr-P3HT-Based Devices

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G. Dennler, M. C. Scharber and C. J. Brabec, Adv Mater, 2009, 21, 1323-1338.

Organic Semiconductors: Key Challenges for
Electron Acceptors in Photovoltaics

High charge-carrier mobility ()

Matching absorption to the solar spectrum (Eg 0.6 - 3 eV)

High negative charge-carrier  (n-type semiconductor)

Processing and morphology

Synthesis of a PCBM Nitrogen Analog

O O
O
C O N O N
O

PCBM 5,6-Open 6,6-Closed

5,6 APCBM 6,6 APCBM

Changduk Yang
Bulk
BulkHeterojunction
HeterojunctionSolar
SolarCell
CellDevice
Device

ITO/PEDOT:PSS/Polym er/Al
P HT : Close
C u rrent D en sity (m A /cm 2)

3
P HT : Open
0 3
P HT : PC BM
3 CLOSE
Voc : 0.58 V
2
Isc : 7.14 mA/cm
-3 Fill Factor: 0.56
OPEN Max Efficiency: 2.3 %
Voc : 0.58 V
2
Isc : 8.10 mA/cm
Fill Factor: 0.60
-6 Max Efficiency: 2.8 %
PCBM
Voc : 0.625 V
2
Isc : 8.11 mA/cm
-9 Fill Factor: 0.66
Max Efficiency: 3.4 %

-0.2 0.0 0.2 0.4 0.6 0.8

Voltage (V)
 The 99’BF Concept

O
1
O
H C9 e
H C9'
1'

99 BF PCBM

99 BF is an electron acceptor because:

•Strain relief between protons H1 and
H1’
Gain in aromaticity
More versatile scaffold
Easier to manipulate
 99’BF Derivatives
RO OR

R R

R R

RO OR R R
6a R = Br
6b R = Cl 1 R = Me 5 3 R=H
6c R = COOMe 2 R = n-C14H29 4 R = OMe
6d R = OMe
λ MAX λ onset HOMO LUMO Eg, CV Eg, optical
(nm)a (nm)b (eV) (eV) (eV)c (eV)d

99’BF 458 513 -5.58 -3.37 2.22 2.42

1 485 536 -5.11 -3.11 2.00 2.31
2 497 542 -5.06 -3.09 1.97 2.29
3 504 560 -5.41 -3.36 2.06 2.21
4 517 569 -5.17 -3.24 1.94 2.18
5 546 603 -5.25 -3.35 1.90 2.05
6c 460 520 -5.38 -3.39 1.99 2.38
6a 458 516 - -3.7 - 2.40
6b 458 515 - -3.7 - 2.41
6c 460 513 - -3.7 - 2.42

F.G. Brunetti, X. Gong, M. Tong, A.J. Heeger, F. Wudl 2009, Angew Chem. submitted
 99’BF Takes Electrons from P3HT

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Xiong Gong, Minghong Tong, Fulvio G. Brunetti, Daniel Moses, F. Wudl, A. J. Heeger 2009,
submitted
 Doubling the Voc !

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Xiong Gong, Minghong Tong, Fulvio G. Brunetti, Daniel Moses, F. Wudl, A. J. Heeger 2009,
submitted
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