Intimate and Mutually Dependent Relationship Between Electrical Energy

Generation, Storage, Distribution, and Efficient Uses

Renewable Energy
Based on solar and wind…
• Intermittent
• Uncontrollable
• Localized

POLICY
Smart Grid & Applications
Electrical Energy Storage
Electricity Distribution & Efficient Usage
“Achilles’s heel of renewable energy” Improve power economy through
• Balance generation and demand • Digital balancing of demand & supply
• Improve power reliability & economy • Solid State Lighting
• Critical for renewable energy • Low power computation
penetration
 Chem. Mater., 2009, 21, 2598.
Adv. Func. Mater., 2009, 19, 2457. JACS, 2009 (DOI: 10.102 / ja9066139)
 New Design Concept for Low Bandgap PV Polymers :
D--A Side Chain Polymers for High Performance Solar Cells
Conventional D-A Polymers New Design Concept

D1 D2 D1 D2 D1

Bridge
Bridge
Eg. A A

CN
C8H17 C8H17
NC

N
n O

O N Increasing
R=
N
S
acceptor
strength
S
O

R
NC
CN

• Facile tuning of energy levels and band gaps

• HOMO level mainly depends on polymer backbone
• LUMO levels tuned by acceptors
Huang, Yip & Jen, J. Am. Chem. Soc., 2009, (DOI: 10.102 / ja9066139)
Optical Properties and Energy Levels for the New Polymers
C8H17 C8H17 Thin film absorption spectrum
N
n

O
O
R= CN
NC O N NC
N
S CN

PF-DCN PF-PDT PF-DCNIO

Potential PCE
HOMO LUMO Bandgap
(eV) (eV)
PF-DCN -5.45 -3.55 1.90

PF-PDT -5.45 -3.7 1.75

PF-DCNIO -5.45 -3.9 1.55

PCBM -6.0 -4.3 1.7

Data from CV and UV-Vis absorption study

Performance of Bulk Heterojunction Polymer Solar Cells
• Hole mobilities of 10-3 to 10-4 cm2/Vs in OFET
• Low lying HOMO (5.45eV) resulted in high Voc of ~1V
• All three polymers show promising OPV performance (as high as 4.8%)

OPV configuration : ITO/polymer:PC71BM w:w = 1:4 (80nm)/Ca/Al

6 100
PF-D C N :P C 71B M
C urrent density (m A /cm )

4 P F-D C N :PC 71 B M
2

PF-PD T:P C 71 B M 80
2 P F-P D T:PC 71 BM
PF-D C N IO :PC 71B M P F-D C N IO :P C 71 BM
0

E Q E (% )
60
-2

-4 40

-6
20
-8

-10
0
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 400 450 500 550 600 650 700 750 800

V oltage (V) W avelength (nm )

FET Hole mobility VOC JSC FF PCE

OPV performance
performance (cm2 V-1s-1) (V) (mA/cm-2) (%)

PF-DCN 1.16E-04 PF-DCN:PC71BM 0.98 9.45 0.49 4.57

PF-PDT 5.18E-04 PF-PDT:PC71BM 0.98 9.42 0.46 4.27

PF-DCNIO 6.70E-04 PF-DCNIO:PC71BM 0.93 7.93 0.47 3.47

Morphological Stability of Polymer / PCBM Bulk Heterojucntions
 Nanoscale phase-separated morphology in bulk heterojunction
P3HT:PCBM film is not very thermodynamically stable
 PCBM has certain freedom to diffuse slowly or re-crystallize over time
especially under elevated temperatures
 This is detrimental to the long-term morphological stability of OPVs

PCBM crystal

Chem. Commun. 17, 2116 (2003) Manca J. et al., Adv. Funct. Mater. 16, 760 (2006)
 Thermally Stable Polymer Solar Cells Using
Amorphous PCBM Acceptors
• Develop amorphous fullerene derivatives to suppress crystallization
• Replace phenylene ring in PCBM with bulky triphenylamine and dimethylfluorene

2
DSC CV
8
PCBM PC BM
PA-PCBM 6

C urrent D ensity (uA )

TPA-PCBM
0 M F-PCBM M F-PCBM
H eat flo w (u W )

Tg =180C 4

-2 2

0
-4 Tg =170C
Crystallization -2
0 50 100 150 200 250 300
o
0 -500 -1000 -1500 -2000 -2500
Tem perature ( C)
V (vs Ag/A g + , m V )

No crystallization for new PCBMs Slightly decrease in LUMO for new PCBMs

Zhang, Yip & Jen, Chem. Mater., 2009, 21, 2598.

BHJ Morphological Stability Under 150°C Annealing
• Thermal annealing of P3HT:PCBMs films at 150°C for different times
• PCBM crystals grow over time
• No sign of crystallization for new PCBM derivatives after 10 hrs of annealing

P3HT : TPA-PCBM
P3HT : PCBM
600 min

200m

P3HT : MF-PCBM
600 min

200m

Zhang, Yip & Jen, Chem. Mater., 2009, 21, 2598.

 Thermally Stable PSCs Using Amorphous PCBM Acceptors
• New PCBMs-based devices shown no degradation after long time annealing
• Important strategy to improve longevity of polymer solar cells
OPV device performance with different annealing time
4 P 3H T :P C B M 4 P3HT :T PA-PC BM
0 m in
C urrent density (m A/cm )

0 m in

C urrent density (m A /cm )

2

2
10 m in 10 m in
P3HT: 0 30 m in
100 m in
0 30 m in
100 m in
PCBM -4
300 m in
600 m in
300 m in
P3HT:
-4 600 m in
TPA-PCBM
-8 -8

-12 -12
-0.2 0.0 0.2 0.4 0.6 0.8 -0.2 0.0 0.2 0.4 0.6 0.8
Voltage (V ) Voltage (V)

5
4 P3H T:MF-P C B M
C urrent density (m A/cm )
2

0 m in
10 m in 4
0 30 m in
P3HT: 100 m in
3
P C E (% )

300 m in
MF-PCBM -4 600 m in
2

-8 P3H T:PC BM
1 P3H T:PA-PCBM
P3H T:M F-PCBM
-12 0
-0.2 0.0 0.2 0.4 0.6 0.8 0 100 200 300 400 500 600
Voltage (V ) Annealing tim e (m in)
 Engineer Interface Using Functional SAMs
• Control charge coupling at interface • Molecular dipole controls
interfacial energy offset

• Control upper layer growth

mode and morphology

• Passivation of inorganic surface traps

ZnO/SAM/Metal Hybrid Cathode for High Performance OPVs

Cathode: Pure Metal

Yip & Jen, Adv. Mater., 2008, 20(12), 2376; APL, 2008, 92, 193314.
Flexible Polymer Inverted Solar Cells with Good Stability
 Superior Inverted OPVs through Integrated Process
Unique device structure that supports all-printing fabrications

5
1.0
ZnO N Ps (No SAM )
ZnO N Ps (C60-SAM )
C urrent D ensity (m A /cm )
2

N orm alized O P V efficiency

0 0.8 Inverted structure

No SAM :  ~3.8% Conventional strcuture
With SAM :  ~4.9% 0.6
-5
0.4

-10 0.2

Flexible solar cell with

0.0
inverted structure
-15
0.0 0.2 0.4 0.6 0 4 8 12 16 20 24 28 32 36 40
V oltage (V ) Tim e (days)

• ZnO provides higher mobility and a room temperature

solution processible option compared to TiO2
Hau, Yip & Jen, APL 2008, 92, 253301.
• ZnO has similar electron trap states that need to be
passivated to improve charge transfer at interface
Huang & Jen, J. Mater. Chem., Cover Page, 2008, 18, 4495. 15
Neutral Conjugated Surfactants as Electron Injection Materials in OLEDs

Cathode
ETL
EML
HTL
ITO
Glass substrate

PFN-OH has the following advantages:

1) The fluorene conjugated backbone has better charge transport ability;
2) Alcohol-based solvents facilitate multilayer PLEDs fabrication;
3) The side chain groups significantly improve electron injection from
high
work-function metals (Al, Ag and Au).
Huang & Jen, Adv. Mater., 2007, 19(15), 2010.
Zhang, Huang & Jen, Adv. Mater. 2008, 20, 1565.
Huang & Jen, Adv. Mater., 2009, 21, 361.
Highly Efficient WPLEDs through Molecular Engineered Surfactants
as Electron-Injecting & Transporting Materials
Device Performance (forward viewing)
Max E.Q.E : 18.3 (%)
Cathode L.E. : 46.6 (cd/A)
Modified surfactant P.E. : 29.1 (lm/W)
EML (white)
Brightness : 19600 (cd/m2) at 15V
PEDOT (30nm) Device Performance (total viewing)
ITO Glass L.E.: 61.4 (cd/A)
P.E.: 49.5 (lm/W)--The best white PLED

CIE (0.36, 0.38)

17
White Solid-state Lighting Developed in Jen Group

18
 Binary and Ternary Materials with E-O activities Beyond the
Saturation Limit of Common Poled Guest-Host Polymers

O
O

O F F
O
F
O Binary chromophore
O F F In self-assembled HDFD
F F

Normalized r33 (a.u.)

O
O
F

F F
Ternary chromophores
in a polymer
Self-assembled HDFD series
Binary chromophores
in a polymer

AJ-TTE-II
in a polymer

AJL8
in a polymer

0 10 20 30 40 50
Kim, Luo & Jen, J. Am. Chem. Soc., 2007, 129, 488. Active Chromophore wt%
Zhou, Luo & Jen, Adv. Mater., 2009, 21(19), 1976.
 Unprecedented E-O Activities Achieved Through
Molecular Engineering and Integrated Center Efforts
STC Developed E-O Materials

Goal
20X better than the
state-of-the-art
inorganic, LiNbO3

Jen, Dalton,
Robinson, Reid

STC/MORPH
 Unprecedented Low Voltage (V) in Hybrid
Polymer / Sol-gel E-O Modulators

Combine low optical loss glass waveguide and high r33 EO polymer

80

70
Y. Enami et al. JLT 21, 2053, 2003
Y. Enami et al. APL 83, 4692, 2003
Packaged hybrid
Y. Enami et al. SPIE 5351, 28, 2004 AJ309 MZ modulator
[V]

Y. Enami et al. APL 89, 143506, 2006

Half Wave Voltage V

60 Y. Enami et al Nature Photon, 1, 3, 180,2007

unpblished
50

40

30

20

10

0
2002 2003 2004 2005 2006 2007
Year

Two Order of Improvements in V Nature Photonics, 2007, 1, 180.

Achieved in STC for Hybrid E-O Appl. Phys. Let., 2007, 91, 093505.
Modulators IEEE Photon. Technol. Let., 2008, 20(12), 1051.

Norwood, Peyghambarian (UA), Luo, Jen (UW)

0.38 V has been realized by Lumera
 A New CMOS Platform - On-Die Optical IO
Photonics on top of CMOS

10 GHz Modulation Speed Demonstrated A

Optical IO

Optical Optical
Layer Layer
Laser

chip chip

B
10010010001
00011101010 Photodetector filter
10110101011 copper

10011011001    

Waveguide silicon nitride

10011010110     CW Laser silicon oxide

00110101011

00101111001 specific Monolithic Integration
modulators -29
10101010011
Optical Layer 0
-31

Normalized Transmission (dB)

-33
-2
Chip (CPU, Memory, Graphics, etc.)
-35
-4

Inensity (dB)
-6
-37
-39
-8

Back end integration of an “optical layer” w/CMOS enables: -41

-10
-43
-12 -20 V  20 V

• High bandwidth -45

1314 1314.1 1314.2 1314.3 1314.4 1314.5 1314.6
• Low power Wavelength (nm)

• Long distance
Block, Younkin, Chang (Intel), Jen (UW), Optics Express, 2008, 16(22), 18326
 Energy Saving in Low Power Computation is Very Significant
(IT accounts for 13% of electricity used today and it will grow to 30-50% in the next decade)

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