AFOSR

Organic Materials Chemistry

18 March 2011

Charles YC Lee
Program Manager
AFOSR/RSA
Air Force Office of Scientific Research
Distribution A: Approved for public release; distribution is unlimited. 88ABW-2011-0803
 2011 AFOSR SPRING REVIEW
230CX PORTFOLIO OVERVIEW
NAME: Charles YC Lee

BRIEF DESCRIPTION OF PORTFOLIO:

To exploit the uniqueness of organic/polymeric materials
technologies for enabling future capabilities currently unavailable by
discovering and improving their unique properties and processing
characteristics

LIST SUB-AREAS IN PORTFOLIO:

Photonic Polymers/Organics
Electronic Polymers/Organics
Permittivity and Permeability Control
NanoTechnology
Others

2
 Research Objective and Challenges

To exploit the uniqueness of organic/polymeric materials technologies

for enabling future capabilities currently unavailable by discovering
and improving their unique properties and processing characteristics

Challenges:
- Discover New Properties
- Control Properties
- Balance Secondary Properties

Approach:
–Molecular Engineering
–Processing Control
–Structure Property Relationship

• Program Focused on developing New and Controlled Properties

• Not applications specific, but often use applications to guide the
properties focuses 3
 Transformational Opportunities
• Reconfigurable Functionalities
Reflective/Absorptive Surfaces

• Conformal Functionalities
• Enable Innovative Applications – Limited
by imagination Conformal Focal
Plane Arrays
• More appropriate for Opportunity Driven,
Not strong in Requirement Pull
• Currently Unavailable Capabilities

Conformal Smart
Plastic Sensor
Skin for Sensors High Fidelity UAV
Carpet for Space 4
and IRCM Control Module
Surveillance
 Other Organizations That Fund
Related Work
• Other Basic Research Organization in this area:
– ONR, ARO, NSF, NIH, DOE
• Other Non-Basic Research Organizations:
– AFRL/TDs, ARL, NRL, DARPA, NRO, DTRA
– DOE, JEIDDO, NIST
• Interactions with Other Agencies
– Federal Interagency Chemistry Representatives Meeting
– Tri-Service Laser Protection Information Exchange Meeting
– Joint AFOSR-ONR Organic Photovoltaic Program Review
– Tri-Service 6.1 MetaMaterials Review
5
 Program Trends

Continued to focus on achieving new functional

Properties
Photonic
Electronic
Magnetic (Spin, Chirality)

New Interests:
Switchable Properties
Decoupling Coupled Properties
Strain effects on Polymer Properties
PT Materials (Parity-Time reversal Materials)

6
 Recent Transitions
TPA 6.1 Results led to AFRL/RX 6.2 Compact Non-Mechanical Beam
and 6.3 Developments Steerer to RW and RY

100% AF240 THF (EX: 375 nm)

EX: 400 nm
EX: 400 nm
Solution EX: 400 nm
Intensity (A.U.)

EX: 375 nm

Thin film
at various locations

400 450 500 550 600 650 700 750

 (nm)

Rewritable 3D Hologram to DARPA Bistable Organic Devices Licensed to

and IARPA Australian startup Sillana for R-RAM
-1

Development
10

“ON” state
-2
10
2nd bias

Current Density (A/cm )

2
-3
10

-4
10

-5
10
1st bias
-6
10
“OFF” state
-7
10

0 0.5 1 1.5 2 2.5 3

Voltage (V)

Electrode Organic layer

Middle Metal
layer 7
Substrate
 Polymer composites with large
permanent conductivity changes
Yi Liao, U of Central Florida

Photochemically or thermally controlling the conjugation and

dopant to control the electronic properties of organic materials.

Nonconjugated Polymer Turn on conjugation Conjugated Polymer

Active or Inactive Dopant Inactive Dopant
INSULATOR Break conjugation SEMICONDUCTOR

Break Deactivate
Turn on
conjugation dopant
conjugation in Activate dopant
the presence of
an active dopant
Conjugated Polymer
Active dopant
CONDUCTOR

8
 Photo-acid generation to convert
non-conducting PA to Conducting PA
H H
N N N N Emeraldine base form of polyaniline
n m INSULATING, conuctivity < 10-8 S/cm

H+

H H H H H
N N N N N N N N
H H H
n m n m

Emeraldine salt form of polyaniline

CONDUCTING.

• Best value in literature shows only 1-2 orders of magnitude improvement

in conductivity even with equal weight of PhotoAcid Generator (PAG)
• Postulate that lack of proton mobility in solid state causes protonation at
the undesirable diphenyl amine location, resulting in break-up of
conjugation.

9
 New Composite to Enhance
Conductivity Changes
Photo Acid Generator

S+ O
-O S CF3 triphenylsulfonium triflate, 254 nm
O

Proton Mobility Enhancer (Polyvinyl alcohol (PVA))

H+
n O+
OH OH OH O+ OH OH O OH
OH H H H H H
PVA A simple illustration of how PVA may increase proton mobility

The left figure shows that

there is an optimized PAG
level. The right figure shows
PAG PVA that too much PVA lowers the
Optimization Optimization
conductivity.

This system was optimized and a 7 order of magnitude conductivity change to 10-2
S/cm can be reproducibly achieved with a optimized PANI-EB/PVA/PAG ratio of
1:1:0.6. (5 orders of magnitude improvement over best values reported in the 10
literature)
 H-Bonding Photo-Acid Generator
(PAG)
HO OH

S+
H-bonding PAG
O
-O S CF3
Preferred Reactive
O
Site
Mixing the H-bonding PAG with PANi N

without PVA or with ~1% PVA can H

N
N
achieve a conductivity of ~10-1 S/cm H
after photoirradiation, which is one O
n

order of magnitude higher than the

S+
previous composite.
H
O N
Effects of Addition of H-bonding PAG H
n
• Prevent aggregation of PAG N
N
• PAG bonded to site for favorable
The PAG can from H-bonding with PANI.
reaction with PANi

11
 Effect of molecular constraints on
optoelectronic behavior of conjugated polymers
Arnold Yang, National Tsing Hua University, Taiwan

The shear flow induced by thin film dewetting instability

was found to induce large PLQE enhancements

Thermal
Dewetting

Solvent
Dewetting
350 30000
As-deposited film Droplet on wafer
Normalized PL intensity (a.u./nm)

300 undewetted film Droplet on glass

25000
Residual films
250
PL intesnity (a.u.)

20000

200
15000
150
10000
100

5000
50

0
0
400 450 500 550 600 650 700
400 450 500 550 600 650 700 12
Wavelength (nm) Wavelength (nm)
 Photoluminescence Enhancement
under stress
OMe

*
MEH-PPV (Poly[2-methoxy- *
H2
C
H
C
n
*

O
n
*
5-((2'-ethylhexyl)oxy)-1,4- Polystyrene
Bu phenylenevinylene])
Et

• PS: MW = 2M g/mol. (disp.

~1.06)
• MEH-PPV: MW = 150~250k
g/mol (disp. ~5)
• film thickness: 0.5mm

Intra-molecular emission Inter-molecular emission

14 14
405 nm 405 nm
12
488 nm
532 nm
Excitation 12
Excitation 488 nm
Enhancement factor (Peak area)

Enhancement factor (Peak area)

532 nm

10 10
Emission: 550 to 575 nm Emission: 580 to 610 nm
8 8

6 6

4 4

2 2

0 0
H-v H-h V-h V-v H-v H-h V-h V-v
13
Polarization of laser + Direction of sample Polarization of laser + Direction of sample
 Chemomechanics: reaction dynamics
under mechanical loads
Roman Boulatov, University of Illinois

Chemomechanical rate law is valid for reactants of any size

Fragmentation of strain-free polymer, ko
ko
Fragmentation of stretched polymer, k(Ft)
k(Ft)
Ft Ft
“weak link”

Macrocycle of Z stiff stilbene: reactive

n monomer is strain-free
Mechanosensitive

m Macrocycle of E stiff stilbene: reactive

monomer is strained
monomer

• Force controlled by linkers

• up to 700 pN in <50 pN increments is
n readily accessible
• Kinetics/mechanism is easy to measure
• Sub-Å positional accuracy of force, ~25 14
m pN force accuracy
 Good Agreement between Experiments
and Theoretical Prediction
Measurements validate the chemomechanical predictions
for bimolecular reactions Reactions:
ln(k(Ft)/ko) Points: experiment; lines: theory
6
acceleration

-2
inhibition

-4

Ft, pN (calculated)
-6
0 200 400 600 15
Direction of tensile force
 Incoherent Light Upconversion
Fil Castellano, Bowling Green State U

Energy Requirements for Sensitized AS Fluorescence

Photoluminescence and Photochemical Upconversion
Based on Sequential Linear Absorption and TT Annihilation
2+

Original
N N
Bimolecular
Prototype:
N Ru N
+
N N

1
An*
[Ru(dmb)3]2+ Anthracene

1
MLCT 3 3
An* + An* (TT Annihilation)
3 Triplet Energy
MLCT Transfer
E
3
An*

•Upconversion with
x 2 incoherent light
•Bimolecular approach allow flexibility in design of
systems and Sperformance
0
parameters
[Ru(dmb)3]2+* + An [Ru(dmb)3]2+ + 3An*
3An* + 3An* 1An* + An
Prof. Felix N. Castellano, Department of Chemistry & Center for Photochemical Sciences, BGSU 16
“Sandwiched” state model originated in 1962: Parker and Hatchard Proc. Chem. Soc. 1962, 386-387.
31
 Improved BODIY Dyes for
Incoherent Upconversion
BODIPY - boron-dipyrromethene
Advantages over Aromatic Hydrocarbons
•High singlet fluorescence quantum yields (Primary)
•Resistance to photobleaching, photooxidation

Photon Upconversion of BD-1 and BD-2 in Benzene, exc = 635 nm

upconversion quantum efficiencies up to 8%

Pt-porphyrin

 triplet sensitizer

N N
N B N
N B N Pt
F F
F F N N

BD-1 BD-2
Ref: Singh-Rachford, Haefele, Ziessel, and Castellano,
17
J. AM. CHEM. SOC. 2008, 130, 16164–16165
Upconversion with Terrestrial Solar
Photons

18
Green to Blue Absorber and
Emitter Combination

N N
Pd

N N

Polyurethane Bar Containing PdOEP

9, 10-diphenylanthracene (DPA) Pd(II)octaethylporphyrin (PdOEP)
Upconverting Polyurethane Bar Containing PdOEP/DPA

Polyurethane Bar

532 nm Laser Pointer

19
 Upconversion in
Glassy Matrix
Chromophores and PMMA were co-extruded from a twin screw
extruder then hot-pressed and quenched into a thin film.
Samples contain ~25% w/w DPA and ~0.25% w/w PdOEP
1.4 x 1.4 cm, 200 mm thick transparent film

250000
PMMA Sample 1.00 Spot #1
Power Density
Spot #1 2
(W/cm )

Upconverted Emission Intensity

200000 0.433
0.356
0.248 0.75
PL Intensity (counts)

0.200
150000
0.120
0.080
0.065
100000 0.038 0.50
0.035

50000
0.25

0
400 425 450 475 500

Wavelength (nm) 0.00

0.00 0.25 0.50 0.75 1.00

Excitation Intensity

PL is linear power dependence at RT

Mechanism of Annihilation is yet unknown 20

 Towards near IR to
Visible Up Conversion
R R

N N N N N N
Zn Zn N Ru N N
N N N N N N

R R Tetracene - Acceptor
R= 2′,6′-bis(3,3-dimethyl-1-butyloxy)phenyl
Pyr1RuPZn2 - Sensitizer

lex = 780 nm, Deaerated MTHF

Anti-Stokes shifted by 0.86 eV 1Tetracene*

MLCT*
ISC
3Tetracene*
3
MLCT* TTET
3 Tetracene* fl = 0.17
em = 505 nm
exc = 780 nm
TTA
3Tetracene*
T = 0.62
tT = 400 ms
GS
ex = 780 nm

New record anti-Stokes shift for sensitized TTA 21

 First Rewritable 3D Hologram

Image recorded using Image reconstructed with dual

polarization multiplexing point source from
technique and reconstructed hologram with one reference.
with white point source.
Nasser Peyghambarian
22
U of Arizona
 Materials for Blue Holograms

Red/Green
Chromophores

Blue Chromophores

PCBM
(sensitizer)
(chromophore)

ECZ PATPD:CAAN
(plasticizer) (transport matrix)
23
6” Sample and Images

24
 One of Top Ten Breakthroughs of
2010 in “physicsworld.com”
Physics World reveals its top 10 breakthroughs for 2010 Dec 20, 2010

8th place: Towards a Star Wars telepresence

Anyone who uses physics to realize a scene from
Star Wars deserves a place in our top 10, which is
why Nasser Peyghambarian and colleagues at the
University of Arizona and Nitto Denko Technical
Corporation come in at number eight. In 1977
audiences were wowed by the special effects in that
cinematic classic, which included a hologram of
Princess Leia making a distress call to Obi-Wan
Kenobi. Now, Peyghambarian and team have taken a F-4
big step towards making such real-time, dynamic
holograms a reality by inventing a photorefractive Phantom
polymer screen that reacts very quickly to laser holograph
light.

-----and Material Chemistry makes it possible----- 25

 Switchable Surface Properties by
Annealing
Anish Tuteja, U of Michigan
Variation in apparent contact angles (*) due to
sequence of annealing treatments in water and dry air
Hexadecane Water
A* ≈ 1.4 A* ≈ 3.9

A 2 mm

Anneal Anneal Filled symbols – advancing contact angles

Half-filled symbols – receding contact angles
in water in air
A ≈ 0.9
* A* ≈ 3.1

W 2
PEMA- poly-ethyl-methacrylate
PEMA –Tg 65oC mm POSS- fluorinated Polyhedral oligomeric silsesquioxane
Annealing Temp 90oC 26
Chhatre et al. Langmuir (2009) 25 (23), 13625-13632.
 PEGDA + fluorodecyl POSS blends
Anish Tuteja, U of Michigan

Surfaces with inherent re-entrant curvature

dip-coated with PEGDA + POSS blends
Pure PEGDA Pure PEGDA
Rapeseed oil
Water Water Rapeseed oil
0º 0º 0º 0º 5 mm
5 mm

10% POSS 10% POSS

A*
0 A*oil  8.5 A*oil  4.3
Rf = -CH2-CH2-(CF2)7-CF3 water A*
water 0

Fluorodecyl POSS 0º 120º 0º 148º

γsv ≈ 8 mN/m 20% POSS 20% POSS
A*oil  8.5 A*oil  4.3
0º 125º 0º 152º

Stainless Steel Wire Mesh Commercial Polyester Fabric

Superhydrophilic and
PEGDA (Polyethylene glycol diacrylate) superoleophobic surface 27
 A Setup for Continuous Oil-Water
Emulsion Separation

500μm

o Water Oil
*  55

Actual Schematic
Setup representation
Hydrophilic / Oleophobic Membrane: PEGDA + 20% fluorodecyl POSS
Hydrophobic / Oleophilic Membrane: PMMA + 20% fluorodecyl POSS
This is the first-ever setup to show continuous gravity based
28
separation of both water-in-oil and oil-in-water emulsions.
 Oil-Water Emulsion Separation

Heat in TGA to 105°C

and hold for 70 minutes
250

200
Flux (L / m hr)

Permeate through HL/OP

2

150
Permeate through HP/OL

100

50

0
0 30 60 90 120 150 180
Time (min)
No decrease in flux due to Very high (> 99%) emulsion
fouling by oil separation efficiency
29
 FMPS method for computational
electromagnetics
Leslie Greengard, NYU
• Meta-material design will require rapid forward modeling
of Maxwell’s equations in complex aperiodic micro-structured materials

– FMPS (Fast Multi-Particle Scattering)

• provides new multiple scattering formalism
• allows for complex particle shapes
• uses rigorous reduced order model for particles

• Far field for each structure expressed in terms of vector spherical

harmonics (Debye potentials/Mie theory)

• Near field computed from solution to Mueller’s integral equation

• Has been coupled with fast multipole (FMM) acceleration

• Will allow for anisotropic inclusions in isotropic background material

• Fully resolved solution, straightforward convergence testing 30 30

Gimbutas, Greengard
 Assemblies of paired NRs
  559nm

•882
25x25x75nm
pairs sep.: 40nm E
k H

•phase:

•standard discretization would involve >1M

degrees of freedom 31 31
 No Difference between Responses
of Periodic & Random structure
25x25x75nm
sep.: 40nm
E-field below paired NR layers
21 x 21 x 2 z    
n  1
d 2
vol. fr.  10% attenuation- negative phase-

Periodic lattice

E
magnitude phase

k H
Random position

32
magnitude phase
 No Difference between Responses
of Periodic & Random structure
At z  3

periodic
lattice

attenuation- -negative phase

magnitude phase

random
 
n  1 position
d 2

magnitude phase
33
-response of periodic & random structure is essentially same!
 Response of Single NRs and Pairs
is Similar
E-field below paired & uniform NR layers
z  
random
position

NR pairs

magnitude phase
random
position

uniform
dist. of
single NRs magnitude phase 34
 High density assembly of NR pairs

  559nm
vol. fr.  10%
d  156nm n  0.58
  42o

 
n  1 magnitude phase
d 2

vol. fr.  34%

d  105nm
n  0.04
  70o

magnitude phase
35
-need vol.fr. ~18% for n=0, vol.fr.>33% for n=-1.
 First Reported Organic Polariton
Lasers
S. Forrest, U Michigan
• Goal: To observe electrically excited lasing in organic semiconductors
• Problem: Excited state (exciton) annihilation prevents electrical pumping of semiconductor lasing
• Approach: Employ exciton-photon coupling in high Q microcavities to create a Bose-Einstein “polariton”
condensate to lase at extremely low threshold.
• Achievement: First demonstration of polariton lasing in an organic material

What is a polariton? Polariton dispersion

uncoupled
cavity dispersion

Energy
uncoupled
exciton dispersion

-E
Ω
strongly coupled state,
microcavity polaritons

In-plane
wavevector
Publication: “Room-temperature Polariton Lasing in an Organic Single Crystal Microcavity”. S. -Kena-Cohen
k
36
and S. R. Forrest, MRS Fall Meeting, invited, Paper O13.4, Boston (Dec. 2, 2009).
 Methods and Results

Below threshold Above threshold

(P=880 pJ) (P=389 nJ)

200 mm 200 mm
37
 Thermodynamic Limit
Brillouin zone
1
N critical  
k 2 / R e  E ( k )  E ( 0 )  / k bT  1
1E14
Polariton Density (cm )
-3

1E13 Polariton
Laser

1E12

Polariton
1E11 LED

1 10 100
Temperature (K)
The critical density at 300K for condensation is ~2x1013/cm3
Threshold is1000X lower than normally pumped lasing 38
Left Blank

39
 Summary

• Program Focused on developing New and Controlled

Properties
• Not applications specific, but often use applications
to guide the properties focuses
• Scientific Challenges
- Discover New Properties
- Control Properties
- Balance Secondary Properties
• General Approaches
- Molecular Design
- Processing Control
- Establish Structure Properties Relationship 40