AFOSR

AFOSR TAIWAN
NANOSCIENCE PROGRAM
(AND AOARD CHEMISTRY)
16 March 2011
Dr. Thomas E. Erstfeld
Program Coordinator
AFOSR/RSZ
Air Force Office of Scientific Research
Distribution A: Approved for public release; distribution is unlimited. 88ABW-2011-0760
A Salute to Our Host!

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 2011 AFOSR SPRING REVIEW
TAIWAN NANOSCIENCE OVERVIEW
NAME: Tom Erstfeld

BRIEF DESCRIPTION OF PORTFOLIO:

Taiwan Nanoscience Program, Chemistry, Materials and Processing,
Technology for the Warfighter

LIST SUB-AREAS IN PORTFOLIO:

NANOSCIENCE – Electronics, Electro-optics, Physics, Chemistry
and Materials Science, Mesoscale Mechanics

CHEMISTRY – All Areas

PARTICULATE MECHANICS – Program with RW

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 Scientific Challenges

• Precise control of materials and their processing at the

atomic/molecular scale will impact everyday life
– Advanced sensing
– Faster, more efficient computing
– Quantum mechanical effects
– The list is endless!
• People are rapidly advancing the state of the art, but –
– What is the underlying physics?
– What knowledge is required to achieve tunablity of
nanomaterials?
– How does one transition from the nanoscale to the
macroscale? What challenges exist in the mesoscale?

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 Transformational Opportunities

• Nanotechnology is progressing rapidly, and no one

knows where it will lead, but its effects will be
worldwide and will be revolutionary
• A few good guesses –
– Nanoelectronic materials
– Components for nano-electromechanical systems
– Realization of quantum computing
– Small, ultrasensitive sensors
– Nanobiology and nano-based medicine

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 Other Organizations That Fund
Related Work

• What organization isn’t funding nanotechnology

research? The list is shorter!
– U.S. National Nanotechnology Initiative spent $1.8B in 2010
– Global public investment estimate of $8.4B in 2008, with a
further $8.6B in corporate funding

• What’s unique about this program

– Influence: Air Force has gained access to some of Taiwan’s
best researchers, and relationships have begun and have
grown; we help guide research directions
– Leverage: the Taiwan Program began in 2003, AOARD has
influenced and harvested the investment of $40M-worth of
Taiwan’s $900M program

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 Program Trends

• Program is making changes in its priorities:

– Stops – Starts
Gallium nitride technology Graphene technology
Medical-related applications Nanofluidics

• The biggest change is in programmatics:

– In FY 2011 integrated proposals from Taiwan and the U.S.
will be required
– Taiwan’s NSC will fund the Taiwan-based partner
– AFRL will fund the U.S.-based partner

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 Representative Projects

• Tin-Based IV-IV Heterostructures

• Polymer Bulk-Heterojunction Solar Cells
• Chemical Reactivity of Complex Systems
• Bio-Inspired Assembly of Artificial Photosynthetic
Antenna Complexes
• Aromatic and Antiaromatic Porphyrinoids

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 Tin-Based IV-IV Heterostructures
Henry Cheng, National Taiwan University

• Scientific objective
– Determine how to integrate photonic or optical devices with Si
• Scientific/technological approach
– Use molecular beam epitaxy (MBE) to create GeSn/Ge
heterostructures to allow integration of direct bandgap devices
into Si platforms

• Breakthrough opportunity
– Use of various alloy compositions of GeSn allows the bandgap
of the materials to be engineered to make devices requiring
tunability or multijunction capabilities

• Partners:
– Coordinating with Gernot Pomrenke, RSE
– Collaborating with Richard Soref, RYH
Greg Sun, University of Massachusetts – Boston 9
 Tin-Based IV-IV Heterostructures

Sn-based IV-IV compounds for direct bandgap TEM image of GeSn film Micrograph at interface:
misfit dislocations
α-Sn 0%

α-Sn 5%

α-Sn ?%

Direct!!!

Momentum (k)
Absorption spectra of GeSn showing
L G
indirect and direct optical transitions
EDS measurement of GeSn
film showing Sn nearly 1.0

STEM image of GeSn film uniformly distributed Bulk Ge

0.8
30

25 0.6 Bulk Ge bandgap

trans
GeSn (2%) (room temperature)
Sn composition (%)

20 0.4

absorption
15
0.2 edge indirect band

10
0.0
5 absorption edge of direct band of GeSn
-0.2
0 0.5 0.6 0.7 0.8 0.9
0 2 4 6 8 10 12 14
10
Energy (eV)
Position (#)
 Tin-Based IV-IV Heterostructures

Theoretical modeling on the energy band of Sn-based disorder effect

on the band gap of GeSn alloys

• Direct gap is observed at

1, 2, 4, 5, 6, 7, and 8 sites
• Formation energy depends
on the number of Sn-Sn
bonds
• Results reveal that growing
conditions and post
treatment of GeSn
• Experimental reports indicate
samples should
direct gap appears at x > 0.112
significantly affect the gap
and 0.1 > x > 0.06
properties of GeSn alloys
• First-principle calculations using
supercell
• Sn is placed as denoted by 1-8
in above figure
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 Polymer Bulk-Heterojunction Solar Cells
Tzung-Fang Guo, National Cheng Kung University (Taiwan)

• Scientific objective
– Determine optimum fabrication techniques for high-performance
solar cells

• Scientific/technological approach
– Use novel interfacial modification in the polymer/electrode
junction to markedly enhance power conversion efficiency

• Breakthrough opportunity
– Improve cell performance through the better collecting efficiency
of the electrodes for the photo-excited charge carriers

• Partners:
– Co-funding provided by Charles Lee, RSA
– Collaborating with Bin Hu, University of Tennessee
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 First BHJ Polymer-Based ODEP Devices

PCBM

rr-P3HT

Optically-induced dielectrophoretic (ODEP) devices 13

Photo Responses of R-G-B Light from Projectors

• High extinguishing coefficient

for P3HT: 9.6 x 105 cm-1 at
530 nm for -* transition)

• Low lateral diffusion for the

precisely and effectively optical
manipulation: low exciton
diffusion length (~10 nm)

• Variable optical responses:

selections of different
conjugated polymers as the
active layer.
• Green illumination has the larger
DEP force due to better overlap with
the absorption of P3HT
Manipulation of Particles by Different Color Rings

A non-contact approach to exclude or collect the polymer particles by shrinking

one of the two light rings with different colors and diameters

Appl. Phys. Lett. 96, 113302 (2010)

 Chemical Reactivity of Complex Systems
Kopin Liu, Academia Sinica (Taiwan)

• Scientific objective
– Understand and ultimately control the reactive outcome of
complex systems by the vibrational excitations of a reactant

• Scientific/technological approach
– Use unique cross-molecular beam apparatus
• Breakthrough opportunity
– Achieve control of chemical reactivity by steric effects
• Other information:
– Co-funding provided by Mike Berman, RSA
– Awarded Alexander von Humboldt Research Award in 2010

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 Chemical Reactivity of Complex Systems

• Reactions of methane with F, Cl,

and O(3P): prototypical of H-atom F + H—CD3 DF + CHD2(11)
abstraction, but with vastly different
energetics and barrier properties
• Exciting a stretching mode of a
x HF + CD3

bond should increase the likelihood

depletion
of the bond breaking
• Study of the F + CHD3 reaction
shows, counter-intuitively, exciting
the C-H bond impedes its breakage
to form HF + CD3
• The rate of the other reaction
pathway – leading to DF and CHD2
– also slows down
• This unexpected finding was
published in Science 325, 303
(2009), and has since received
wide publicity in C & E News,
RSC Chemistry World, and Nature
Chemistry formation 17
 O
F
D D

C H O C H F
D D
D D
O F

Exciting the C-H stretch of CHD3 reactant induces

precisely opposite steric-effects on chemical reactivity !
O(3P) + CHD3: focusing effect  enlarging the reactive
cone of acceptance
F(2P) + CHD3: defocusing  hindrance of the overall
reaction rate, particularly the HF channel
 Bio-Inspired Assembly of Artificial
Photosynthetic Antenna Complexes
Mamoru Nango, Nagoya Institute of Technology (Japan)

• Scientific objective
– Use natural photosynthetic process to produce low-cost sensors
with inherently high photon-capturing and charge-separation
efficiencies

• Scientific/technical approach
– Control the direction and orientation of photosynthetic antenna
pigment complexes on electrodes

• Breakthrough opportunity
– Develop sensors having light-conversion efficiency into
chemical energy of nearly 100%

• Partners:
– Co-funding provided by Hugh DeLong, RSL
– Collaborating with Minoru Taya, University of Washington 19
The X-ray structures and AFM image of antenna complexes from purple photosynthetic bacteria

LH2 complex from Rps. acidophila 10050 LH1-RC core complex from Rps. palustris AFM Image
LH-b

BChl a

carotenoid LH2
LH-a & -b /
LH1-RC
LH-a BChl a
~6.8nm ~11nm
R.J. Cogdell, et. al, Nature, 374, 517 (1995) R.J. Cogdell, et al., Science, 302, 1969 (2003)

N N
Mg
N N
Bacteriochlorophyll a
O
(BChl a)
COOCH3
O
O

OCH3 The antenna complexes efficiently realize various

photosynthetic functions using cofactors (BChl a
OCH3
Carotenoid and carotenoid) assembled into the apoproteins:
The energy conversion yield is ~100%
 Assembly of LH2 onto line-patterned substrate
Au: 20 nm

5 mm
Etching
Absorption spectra of LH2
Au on SiO2 0.6


0.5 solution
In 0.002

Absorbance
0.4
Patterned substrate 0.3
0.001


0.2
for organization of 0.1
0.0 On substrate0.000
LH2 and LH1-RC -0.1
700 800 900
Wavelength/nm
Bright Field Epi-FL

A clear fluorescence of LH2 with SH-tag was

observed at the Mal sites on the substrate with
lined patterning when illuminated at near IR region
(right figure) 40 mm 40 mm

On-going:
SiO2 Fluorescence (LH2)
LH1-RC with His-tag will be further assembled on Au
the NTA site to produce an efficient energy transfer
from LH2 to LH1-RC on the substrate for
development of new type of nanosensors and
nanosemiconductors (nanobiophotonics)
 Aromatic and Antiaromatic Porphyrinoids
Dongho Kim, Yonsei University (Korea)
Atsuhiro Osuka, Kyoto University (Japan)

• Scientific objective
– Systematically propose, synthesize, and characterize promising
candidate molecules having large third-order non-linear optical
properties

• Scientific/technological approach
– Atsuhiro synthesizes expanded porphyrins, while Dongho
performs a myriad of femtosecond spectroscopic analyses

• Breakthrough opportunity
– Improved eye-protection from lasers, advanced photocatalysts
• Partners:
– Co-funding provided by Charles Lee, RSA, and Tom Cooper, RXP

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Aromatic and Antiaromatic Porphyrinoids

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 Aromatic and Antiaromatic Porphyrinoids

Hückel Aromaticity

Hückel topology MO energy levels

Hückel topology MO energy levels

28 

Double-sided
[4n+2]  : aromatic Antiaromatic
Double-sided [4n] : antiaromatic
Möbius topology [4n+2]  : aromatic
Möbius Aromaticity [4n] : antiaromatic
Möbius topology

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[4n+2]  : antiaromatic
sign inversion Single-sided
[4n]  : aromatic
[4n+2]  : antiaromatic
sign inversion Single-sided
[4n]  : aromatic Aromatic

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Aromatic and Antiaromatic Porphyrinoids

First time that the

physical and chemical
properties of various
expanded porphyrins
have been closely
related to aromaticity

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 Recent Transitions

• Tin-Based IV-IV Heterostructures

– Transitioned to Richard Soref, RYH
• Aromatic and Antiaromatic Porphyrinoids
– Supported by and transitioned to Tom Cooper, RXP
• Passivation of Indium Arsenide and Gallium
Antimonide High κ Dielectrics
– Supported by and transitioned to Gail Brown, RXP
• Particulate Mechanics
– Supported by and transitioned to Lalit Chhabildas and Bill
Cooper, RWM

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 The Future

• New business model for the Taiwan Nanoscience

Program in 2011
– Program is based on model used for Korea NBIT Program:
 Ensures partnerships
 Ensures transitions
 Secures Taiwanese investment

• Increased emphasis on chemistry

– Reaction Dynamics
– Catalysis
– Ionic Liquids
– Biochemistry
– Synthesis
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Questions?

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