UCSB Craig Hawker. Commercial Applications of Polymer as Nanomaterials
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1. Craig J. Hawker Commercial Application of Polymers as
Nanomaterials
2. Research Philosophy Research Philosophy To effectively use
Polymers as Nanomaterials To effectively use Polymers as
Nanomaterials it is ESSENTIAL to accurately it is ESSENTIAL to
accurately manipulate chemical structure and architecture
manipulate chemical structure and architecture
3. Robust, Efficient, and Orthogonal Chemistry Robust,
Efficient, and Orthogonal Chemistry Prof. K. Barry Sharpless Prof.
K. Barry Sharpless Prof. Sir John Cornforth Prof. Sir John
Cornforth Need Robust, Efficient, and Orthogonal Chemistry to Need
Robust, Efficient, and Orthogonal Chemistry to prepare
functionalized polymers for Nanoscale Applications prepare
functionalized polymers for Nanoscale Applications
4. Recent Examples of Efficient Chemistry Recent Examples of
Efficient Chemistry Click Chemistry Click Chemistry --nanoparticles
for diagnosis and nanoparticles for diagnosis and treatment of
cardiovascular disease treatment of cardiovascular disease LFRP
Polymerization LFRP Polymerization --block copolymer lithography
block copolymer lithography Isomerization Isomerization --films for
holographic storage films for holographic storage
5. Challenges in NanoMedicine CANCER CANCER 1.4 million cancer
cases (2006) 1.4 million cancer cases (2006) 560,000 deaths
expected (2006) 560,000 deaths expected (2006) Earlier detection
strategies $210 billion (2005) $210 billion (2005) and novel
therapeutic approaches could help HEART DISEASE HEART DISEASE
reduce surgical costs and 71.3 million Americans (~1:3 adults) 71.3
million Americans (~1:3 adults) increase the quality of life
910,000 deaths (2003) 910,000 deaths (2003) $403 billion (2006)
$403 billion (2006) Courtesy of American Cancer Society and
American Heart Association
6. Targeted Nanoparticles for Vascular Injury Targeted
Nanoparticles for Vascular Injury Injury causes rupture of
endothelium Injury causes rupture of endothelium and exposure of
smooth muscle cells and exposure of smooth muscle cells which
over-express binding molecules which over-express binding molecules
at surface v3 v5 at surface v3 v5 Target platlets --IIv3 Target
platlets IIv3
7. Multi-functional Nanoparticles Multi-functional
Nanoparticles Cell transduction component permeation peptide
Targeting component for cell surface antibody or small molecule
Therapeutic payload drug, protein or gene Detection Element
radionuclide, MRI agent, or optical chromophore Targeting component
for intracellular mRNA PNA
8. Multi-functional Nanoparticles Multi-functional
Nanoparticles Design Criteria - Nanoparticles 1) Must have long
blood circulation lifetimes 2) Attach diagnostic agents surface or
interior 3) Functionalize with targeting ligands surface 4)
Incorporate therapeutics interior 5) Design biodegradability
9. Synthesis of Nanoparticles Synthesis of Nanoparticles + +
Latent functionality PEG: 1kDa 10 kDa PEG: 1kDa 10 kDa 120oC For
5kDa PEG For 5kDa PEG Mn = 17 kDa; PDI = 1.08 Mn = 17 kDa; PDI =
1.08 Arm copolymer
10. Synthesis of Nanoparticles Synthesis of Nanoparticles + +
Cross-linker -X- = or NMP 120oC Arm copolymer Mn = 17 kDa; PDI =
1.08 Mn = 17 kDa; PDI = 1.08 Hydrophobic Hydrophobic PEG shell for
PEG shell for Core Core biocompatibility biocompatibility Mn = 690
kDa; PDI = 1.18 Mn = 690 kDa; PDI = 1.18 Reactive Reactive Internal
Groups Internal Groups Star copolymer
12. Size Distribution of Nanoparticles 5kDa --PEG Arm (MW:
17kDa) 5kDa PEG Arm (MW: 17kDa) 2kDa PEG Arm (MW: 11kDa) 2kDa PEG
Arm (MW: 11kDa) DVB core DVB core EGDA core EGDA core DVB core DVB
core EGDA core EGDA core Dh = 60 nm 49 nm 35 nm 26 nm Can control
size, % of PEG, position and number of functional groups
13. Size Distribution of Nanoparticles 5kDa --PEG Arm (MW:
17kDa) 5kDa PEG Arm (MW: 17kDa) Darrin Pochan --Delaware Darrin
Pochan Delaware EGDA core EGDA core 49 nm Cryo-TEM shows core shell
structure and relative monodispersity
14. Multi-functional Nanoparticles Multi-functional
Nanoparticles Design Criteria - Nanoparticles 1) Must have long
blood circulation lifetimes 2) Attach diagnostic agents surface or
interior 3) Functionalize with targeting ligands surface 4)
Incorporate therapeutics interior 5) Design biodegradability
15. Positron Emission Tomography (PET) Positron Emission
Tomography (PET) Annihilation Annihilation 511 keV 64Cu Gamma Ray
Positron + e- Electron 511 keV Gamma Ray The radionuclide decays
and the resulting positrons subsequently annihilate on contact with
electrons after traveling a short distance within the body Each
annihilation produces two 511 keV photons traveling in opposite
directions (~180) which are detected by the detectors surrounding
the subject Karen Wooley, Mike Welch, Carolyn Anderson
16. DOTA Conjugation and 64Cu Labeling 64Cu properties COO-
12.7 hr half-life N Decays by + (positron, PET imaging) and - (Beta
particle, radiotherapy) O N O N Cu O DOTA properties O FDA approved
chelator N Also used for Gd (MRI) COO- Readily chelates metal
cations
17. Synthesis of DOTA-amine Synthesis of DOTA-amine HBTU, NHS
TEA, DMF, R.T. 91% H2, Pd/C EtOH / THF HBTU 90% Nature and length
of linker Nature and length of linker affects 64Cu chelation
affects 64Cu chelation
18. DOTA Conjugation into Star Copolymer Optimize structure and
Optimize structure and function of nanoparticles function of
nanoparticles --BioD BioD DOTA-amine DMF, R.T., 30h
19. Labeling with 64Cu Labeling with 64Cu 1. TFA DOTA-amine
Cu2+ 2. DMF, R.T., 30h 64Cu 64Cu
20. Techniques for Biodistribution/microPET Techniques for
Biodistribution/microPET 70 60 50 40 30 20 10 0 lung liver kidney
spleen muscle heart blood bone fat
21. BioDistribution with diblock copolymer arm BioDistribution
with diblock copolymer arm 100 10m i n 1h 4h 24h 48h 80 % I / gan
60 D or Arm copolymer 40 Mn = 17 kDa; PDI = 1.08 Mn = 17 kDa; PDI =
1.08 20 0 Bl Fe Li Lu Sp Ki U rn ve oo dn i ce ng lee r e d ey s
n
22. BioDistribution with star based on 2kDa PEG BioDistribution
with star based on 2kDa PEG 100 10m i n 1h 4h 24h 48h 80 % I / gan
60 D or Mn = 490 kDa; PDI = 1.19 Mn = 490 kDa; PDI = 1.19 40 20 0
Bl Fe Li Lu Sp Ki U rn ve oo dn i ce ng lee r e d ey s n
23. BioDistribution with star based on 5kDa PEG BioDistribution
with star based on 5kDa PEG 100 10m i n 1h 4h 24h 48h 80 % I / gan
60 D or Mn = 510 kDa; PDI = 1.18 Mn = 510 kDa; PDI = 1.18 40 20 0
Bl Fe Li Lu Sp Ki U ri ve oo dn ce ng l ne ee r d ey s n Higher
& longer blood circulation Much lower uptake in liver
25. CT/PET Imaging of 5kDa PEG Stars CT/PET Imaging of 5kDa PEG
Stars 5kDa Stars injected in aanormal Sprague-Dawley rat (top) and
in aaBalb/C mouse (bottom) 5kDa Stars injected in normal
Sprague-Dawley rat (top) and in Balb/C mouse (bottom) 1h
post-injection 4h post-injection
26. Targeted Nanoparticles Targeted Nanoparticles Injury causes
rupture of endothelium Injury causes rupture of endothelium and
exposure of smooth muscle cells and exposure of smooth muscle cells
which over-express binding molecules which over-express binding
molecules at surface v3 at surface v3
27. Multi-functional Nanoparticles Multi-functional
Nanoparticles Design Criteria - Nanoparticles 1) Must have long
blood circulation lifetimes 2) Attach diagnostic agents surface or
interior 3) Functionalize with targeting ligands surface 4)
Incorporate therapeutics interior 5) Design biodegradability
29. Synthesis of Nanoparticles Synthesis of Nanoparticles + +
Cross-linker -X- = or NMP 120oC Arm copolymer Hydrophobic
Hydrophobic PEG shell for PEG shell for Core Core biocompatibility
biocompatibility Orthogonal Reactive Orthogonal Reactive Reactive
Reactive Terminal Groups Terminal Groups Internal Groups Internal
Groups Mn = 550 kDa; PDI = 1.16 Mn = 550 kDa; PDI = 1.16
30. DOTA Conjugation into Star Copolymer DOTA-amine DMF, R.T.,
30h
31. Click Chemistry Click Chemistry R 1 R1 H H ++ N N N N N N
R2 R 2 - + CuSO 4 50 kcal driving force 50 kcal driving force
reducing agent rt - water 1 1 :: 1 1 R1 H R1 HH R1 ** Compatibility
with ** Compatibility with + ** Quantitative ** Quantitative
functional groups N N functional groups R N 2 N NR N Ryields yields
2 N N 2 N
32. Peptide functionalization Click reaction with acetylenes
Click reaction with acetylenes --modular chemistry modular
chemistry Azide-Gly-Gly-Gly-Arg-Gly-Asp-Ser-Pro-Amide
Azide-Gly-Gly-Gly-Arg-Gly-Asp-Ser-Pro-Amide
Azide-Gly-Gly-His-His-Ley-Gly-Gly-Ala-Lys-Gln-Ala-Gly-Asp-Val-Amide
Azide-Gly-Gly-His-His-Ley-Gly-Gly-Ala-Lys-Gln-Ala-Gly-Asp-Val-Amide
Jeff Smith - Burnham
33. Peptide functionalization COO- N O N O N Cu O O N COO-
Peptides-N3 Click * Quantitative Yields * Quantitative Yields *
Mild reaction conditions * Mild reaction conditions
34. CT/PET Imaging of Targeted 5kDa PEG Stars CT/PET Imaging of
Targeted 5kDa PEG Stars Injured Carotid Injured Carotid 64Cu-5kDa
PEG nanoparticle with c-RGD 64Cu-5kDa PEG nanoparticle with c-RGD
targeting 5h post-injury targeting 5h post-injury No statistical
differences with post-injury No statistical differences with
post-injury imaging times imaging times 15% of chain ends labeled
ca. 6 c-RGD units 15% of chain ends labeled ca. 6 c-RGD units v 3
Competitive Binding Assay Binding affinity for vv3(IC50): 6.4 nM
Binding affinity for 3 (IC50): 6.4 nM 100 % Vitronectin Activity 75
Affinity for vv5(IC50) > 10,000 nM Affinity for 5 (IC50) >
10,000 nM 50 25 No targeting groups --Affinity for No targeting
groups Affinity for vv3and vv5(IC50) > 15,000 nM 3 and 5 (IC50)
> 15,000 nM 0 -3 -2 -1 0 1 2 3 4 Log [Nanoparticle]
35. Imaging of Arterial Injury with 5kDa PEG Stars Imaging of
Arterial Injury with 5kDa PEG Stars Arterial Injury Arterial Injury
R L ** 600% increase in ** 600% increase in detection level
detection level RGD-star NP Control star NP Sham Injury Sham
Injury
36. Microelectronics Microelectronics *** drive to 45 nm and
smaller *** drive to 45 nm and smaller Procedures are needed to
allow sub 50 nm lithography Procedures are needed to allow sub 50
nm lithography -- Low Cost Low Cost -- Compatible with Current
Manufacturing Compatible with Current Manufacturing
37. * NEED K < 2.0!!!!! * NEED K < 2.0!!!!! Dielectric
Dielectric materials materials SiO22 SiO K = 4.0!!! K = 4.0!!! AIR
AIR 300 nm K = 1.01?? K = 1.01??
38. Need Low K materials -- K < 2.0 -- porosity!!!! Need Low
K materials K < 2.0 porosity!!!!
39. Air Gap Manufacturing Air Gap Manufacturing Cu lines
Dielectric Deposit Template Size of holes is Critical < 20nm
Size of holes is Critical < 20nm Form Holes Remove Dielectric
Pinch off Holes --Low Cost Low Cost Build --Compatible with
Compatible with Multilayers Current Manufacturing Current
Manufacturing
41. Comparison: Lithography vs. Self Comparison: Lithography
vs. Self Assembling Block Copolymers Assembling Block Copolymers
Critical steps Critical steps 1. Neutralization 1. Neutralization
of surface of surface Expensive Expensive Photolithography
Photolithography 2. Vertical alignment 2. Vertical alignment of
PMMA cylinders of PMMA cylinders 3. Photochemical 3. Photochemical
removal of removal of PMMA cylinders PMMA cylinders
42. Assembling a thin-film polymer template Assembling a
thin-film polymer template Tom Russell -- UMASS Tom Russell UMASS
Block Block Copolymer Copolymer ** Critical to make cylinders
vertical not horizontal ** Use neutral layer ** Use neutral
layer
43. Control of Surface Properties Control of Surface Properties
PMMA PS NEUTRAL SURFACE NEUTRAL SURFACE NEUTRAL SURFACE NEUTRAL
SURFACE 42 58 50 50 100% PS MMA STY RANDOM COPOLYMER RANDOM
COPOLYMER 100% PMMA STRUCTURES STRUCTURES
44. Random Copolymer Random Copolymer . O - O N Zn/HOAc +
PhMgBr NO2 + CHO N Jacobsen's Reagent Routinely made on kg scale
Routinely made on kg scale Cl N O N N O O O OMe 58% Sty 1. NaOAc
42% MMA 2. KOH 58 42 OH OH Cl Surface attachment
45. Formation of Random Copolymer Brush Formation of Random
Copolymer Brush OH OH OH OH OH OH OH OH Si Si Si Si Si Si Si Si
Neutrality at Neutrality at O N 58% styrene HEAT HEAT 58% styrene
and 42% MMA 12 hours 12 hours O OMe and 42% MMA 58 42 OH
46. Effect of Surface Preparation Effect of Surface Preparation
No surface preparation No surface preparation NORMAL NORMAL PS-PMMA
random PS-PMMA random (native oxide //silicon) (native oxide
silicon) PS-PMMA copolymer copolymer --LFRP PS-PMMA copolymer
copolymer LFRP * * random copolymer neutralizes surface for random
copolymer neutralizes surface for proper diblock copolymer
self-assembly proper diblock copolymer self-assembly
47. Comparison: Lithography vs. Self Comparison: Lithography
vs. Self Assembling Block Copolymers Assembling Block Copolymers
Critical steps Critical steps 1. Neutralization 1. Neutralization
of surface of surface Expensive Expensive Photolithography
Photolithography 2. Vertical alignment 2. Vertical alignment of
PMMA cylinders of PMMA cylinders 3. Photochemical 3. Photochemical
removal of removal of PMMA cylinders PMMA cylinders
48. Air Gap Air Gap
49. Press Coverage Press Coverage IBM's chip breakthrough comes
from IBM's chip breakthrough comes from tiny holes. May 4, 2007
tiny holes. May 4, 2007 Chips with minuscule holes in them can run
faster Chips with minuscule holes in them can run faster or use
less energy, IBM said in announcing aanovel or use less energy, IBM
said in announcing novel way to create them potentially one of the
most way to create them potentially one of the most significant
advances in chip manufacturing in significant advances in chip
manufacturing in years. years. To create these tiny holes, the
computer company To create these tiny holes, the computer company
has harnessed aaplastic-like material that has harnessed
plastic-like material that spontaneously forms into aasieve-like
structure. spontaneously forms into sieve-like structure. quot;To
our knowledge, this is the first time anyone quot;To our knowledge,
this is the first time anyone has used nanoscale self-assembled
materials to has used nanoscale self-assembled materials to build
things that machines aren't capable of doing,quot; build things
that machines aren't capable of doing,quot; said John Kelly, IBM's
vice president of said John Kelly, IBM's vice president of
development. development.
50. Challenges to Manufacturing Challenges to Manufacturing 1.
Neutral brush 1. Neutral brush step is slow step is slow 12 to 16
hours 12 to 16 hours Critical step Critical step Critical steps
Critical steps 2. Regularity 2. Regularity
51. 1. Replace Polymer Brush 1. Replace Polymer Brush Improved
Manufacturability Improved Manufacturability Polymer Brush Polymer
Brush --very slow formation very slow formation Crosslinked Thin
Film Crosslinked Thin Film -- very robust very robust -- quick
formation quick formation
52. Chemistry Chemistry * Based on Benzocyclobutene (BCB)
chemistry * Based on Benzocyclobutene (BCB) chemistry o-quinoid
structure is o-quinoid structure is extremely reactive extremely
reactive BCB ring is unreactive BCB ring is unreactive + OTHER
PRODUCTS Coupled product is Coupled product is extremely stable
extremely stable
53. Improved Manufacturability Improved Manufacturability N O N
H O H 120 C + + + O OMe O OMe x y z 3mol% BCB 3mol% BCB 55mol% Sty
55mol% Sty 42mol% MMA 42mol% MMA Spin-coat 250 C O OMe x y z
Crosslink O OMe OMe O x y z z y x ** Simple spin-coat then bake
procedure ** Simple spin-coat then bake procedure
54. Improved Manufacturability Improved Manufacturability 12 10
Thickness (nm) 8 12 10 Thickness (nm) 6 8 6 o 200 C 4 4 o 250 C 2 2
0 0 5 10 15 20 25 30 Time (hr) 0 0 1 2 3 4 Time (hr) ** less than
10 minutes bake time at 250C gives robust films ** less than 10
minutes bake time at 250C gives robust films
55. Process Variability Process Variability Bare Bare Coated
with 66nm Coated with nm Substrate Substrate PSt-BCB-PMMA copolymer
PSt-BCB-PMMA copolymer Al 36.1 o 76.3 o SiN 31.5 o 76.2 o Kapton
53.6 o 75.8 o PET 65.3 o 75.9 o ** Examine water contact angles **
Examine water contact angles
56. Process Variability Process Variability Thermal evaporation
of Au on Au 19 Au on Si 35 nm Si 6 Block Copolymer Crosslinked
P(S-r-BCB-r-MMA) Crosslinked P(S-r-BCB-r-MMA) Block Copolymer +
Block Copolymer + Block Copolymer on Au on Si on Au on Si **
Process is substrate independent!! ** Process is substrate
independent!!
57. Regularity Regularity 300mm wafer edge Current process --
PSt-PMMA Current process PSt-PMMA -- Defects and Grain Boundaries
Defects and Grain Boundaries -- Limits applications Limits
applications
58. Regularity CHANGE block polymer Regularity CHANGE block
polymer PSt-PMMA PSt-PMMA PSt-PEO PSt-PEO Cannot degrade PEO!!!
Cannot degrade PEO!!! High degree of order and High degree of order
and possible REGISTRATION possible REGISTRATION opens up NEW
possibilities opens up NEW possibilities ** Absence of Grain
Boundaries over Large Dimensions Absence of Grain Boundaries over
Large Dimensions ** PEO-PSt block allows 7-8 nm features PEO-PSt
block allows 7-8 nm features
59. Incorporate New Complexity into Blocks Incorporate New
Complexity into Blocks O MeO OH + MeO O OH O O n O O O n O O N H
DCC/DPTS Cleavable Cleavable OH Ester Linkers Ester Linkers H O N
MeO O O O O n O o Design Function into Block Design Function into
Block 100 C Copolymers through Chemistry Copolymers through
Chemistry N3 O MeO O O O N O n O H x y Photochemical crosslinkable
group Photochemical crosslinkable group N3
60. 2. Regularity 2. Regularity PEG PS * new block copolymer
PEG-PSt substrate Spin Spin copolymer substrate copolymer h h
X-linked PS X-link azides X-link azides TBAH TBAH substrate Removes
PEG Removes PEG -- NO RANDOM copolymer NO RANDOM copolymer --
Normal Photoresist developer Normal Photoresist developer
61. 2. Regularity 2. Regularity PEG PS * new block copolymer
PEG-PSt OH- OH- substrate Spin Spin copolymer substrate copolymer
Sharp Sharp Interfaces Interfaces O MeO O O O OH- n O O PSt MeO O O
O n O O PSt NO degradation NO degradation MeO O O n O O O PSt MeO O
O O PSt NO Template NO Template MeO O n O O O O n O O PSt MeO O O O
PSt Ester groups are not n O O Ester groups are not MeO O O n O O O
PSt sufficiently available for hydrolysis sufficiently available
for hydrolysis MeO O O n O O PSt
62. Improving Long Range Order Improving Long Range Order
PS-b-PMMA: long-range order Make Triblock Make Triblock Copolymer
Copolymer PS PEO PMMA PS-b-PEO: degradability UV irradiation UV
irradiation Nanoporous films with arrays of well-ordered
nanopores
63. ABC Triblock Copolymers ABC Triblock Copolymers Bring
richer nanostructures and unique Bring richer nanostructures and
unique properties to Block Copolymer Lithography properties to
Block Copolymer Lithography
65. Synthesis of Triblocks Synthesis of Triblocks DCC, DPTS
DMAP O O OH O n O Br Br OH O n O S MgBr + CS2 S- O Synthesis of
Synthesis of O S O n PEG-macroinitiator PEG-macroinitiator S
66. Synthesis of Triblocks Synthesis of Triblocks O O O S O O S
OMe O n m O n S AIBN, Benzene O S 70 oC O Benzene 70 oC O O S O n m
p O S PEG-triblocks PEG-triblocks O Mn (PSt) = 40K; Mn (PMMA) =
12K; Mn (PEO) = 5K Mn (ABC) = 57K; PDI = 1.08
67. Characterization of Triblocks Characterization of Triblocks
O b NMR c O S O n a PEG-macroinitiator S b c a O O S O m p n O S
PEG-triblock O 100 % functionality of the end group SEC PEO-PMMA-PS
(5k-1.5k-13.5k) Narrow distribution (Mn/Mw < 1.1) PEO-PMMA
(5k-1.5k) PEO (5k) 12 13 14 15 16 17 18 Elution time (min)
68. Low MW PMMA High MW PMMA PEO Crystals Separate Separate PEO
Crystals PMMA/PEO PMMA/PEO domains domains Amorphous Amorphous PEO
too short PEO too short PMMA/PEO PMMA/PEO to crystallize to
crystallize blend blend No PORES No PORES PORES PORES ** Nature of
nanostructure critical for function
69. Porous Block Copolymer Templates Porous Block Copolymer
Templates AFM AFM TEM TEM PEO(5K)-PMMA(6K)-PS(32K) 400 nm 200 nm
Pores traverse completely through film
71. Market leader in Holographic Storage Market leader in
Holographic Storage Holographic drive Holographic disc
(tapestry300r) 20MB/s transfer rate 1.5 mm recording material WORM
recording format 130 mm diameter disk 405 nm laser wavelength 50
year archive life $18,000.00 Capacity = 300GB native $180.00
Inphase Technologies, Longmont, Colorado 80501, USA
72. 2-Stage Chemistry for InPhase System 2-Stage Chemistry for
InPhase System SH OH OH O SH O O O O HS O O O HO O HO O O O n O n
OH O OH S HS O S O n Matrix precursor I n HO O HO O epoxy matrix O
O Hologram O S O O formation recording S O O S O O O O O O S O OH O
O n OH O S O O S HO O Matrix precursor II HO n O n O O O OH O OH O
n n HO Monomer HO Monomer Initial Formulation Holographic Disc Data
Storage
73. Merit and Drawbacks of InPhase Technology Merit and
Drawbacks of InPhase Technology Advantages + High sensitivity +
High storage capacity Disadvantages - Shrinkage of the material due
to monomer diffusion image distortion - Polymerization inhibition
due to oxygen and other inhibitors - Need of pre-exposure to remove
inhibitors dynamic range reduction - Phase separation if the
resulting polymer is not compatible with the matrix material low
archival-life - low thermal stability of the material low
shelf-life .holographic data storage is in aapeculiar situation:
Research on recording devices and recording .holographic data
storage is in peculiar situation: Research on recording devices and
recording schemes has far progressed further than the development
of the required materials; they constitute schemes has far
progressed further than the development of the required materials;
they constitute aabottleneck for the development of the technology.
bottleneck for the development of the technology. Stephan J. Zilker
(CHEMPHYSCHEM, 2002, 3, 333) Stephan J. Zilker (CHEMPHYSCHEM, 2002,
3, 333)
74. Quantum Amplification Approach to Holography h Hexamethyl
Dewar benzene Hexamethyl benzene Photoinduced isomerization leads
to change in the electronic structure and the geometry of the
molecule + No new bonds are forming No shrinkage + One photon
isomerizes more than one dewar benzene high sensitivity + No
developing step needed Evans, T. R.; Wake, R. W.; Sifain, M. M.;
Tetrahedron Lett. 1973, 9, 701.
76. Angular Selectivity Angular Selectivity 2.0 60 1.8
diffraction efficiency (%) 50 1.6 1.4 40 1.2 30 1.0 0.8 20 0.6 10
0.4 0 0.2 0.0 20 22 24 26 28 30 32 20 22 24 26 28 30 32 angular
selectivity (degrees) angular selectivity (degrees) * High
diffraction efficiency * Well-defined nulls * Can store large
amounts of information
77. Angular Multiplicity Angular Multiplicity 3.0 8 7 2.5
diffraction efficiency (%) 6 2.0 Cumulative M/# 5 1.5 4 3 1.0 2 0.5
1 0 0.0 12 16 20 24 28 32 36 0 50 100 150 200 250 300 350 400 2
Cumulative Exposure Energy (mJ/cm ) angular selectivity (degrees)
each hologram was recorded by 6 sec exposure to the writing beams
sharpness and symmetry of the curves indicate the high resolution
that can be achieved by QAI Gen II (UCSB) imaging system ***
Comparable performance to InPhase simplified processing ***
Comparable performance to InPhase simplified processing
78. Shelf-life comparison Shelf-life comparison 3.0 2.5 2.0 M/#
2 weeks 1.5 2 weeks 1.0 0.5 0.0 0 2 4 6 8 10 12 time (weeks)
Photopolymer QAI System (UCSB) 80% decrease in storage No change in
storage capacity capacity after 2 weeks of formulation after 12+
weeks of formulation (Chem. Mater. 2000, 12, 1431)
79. Conclusions Conclusions * * Efficient chemical
transformations are Efficient chemical transformations are
important in the design of new materials important in the design of
new materials * * For either microelectronic, data storage and For
either microelectronic, data storage and energy applications must
control structure energy applications must control structure
different structures give different performance different
structures give different performance
80. Thanks!!! Thanks!!! UCSB Luis Campos, Jasmine Hunt, Nalini
Gupta, Kenichi UCSB Luis Campos, Jasmine Hunt, Nalini Gupta,
Kenichi Fukukawa, Eric Pressly, Ashley Mynar, Ben Messmore, Eic
Fukukawa, Eric Pressly, Ashley Mynar, Ben Messmore, Eic
Drockenmuller, Chuanbing Tang, Joona Bang, Matt Kade, Katie
Drockenmuller, Chuanbing Tang, Joona Bang, Matt Kade, Katie
Schaefer, Ed Kramer. Schaefer, Ed Kramer. WUStL Karen Wooley, Mike
Welch, Dan Schuster, Dana WUStL Karen Wooley, Mike Welch, Dan
Schuster, Dana Abendschein, Carolyn Anderson, Raffa Rossin, Ashley
Fiamengo, Abendschein, Carolyn Anderson, Raffa Rossin, Ashley
Fiamengo, Amir Hagoolya. Amir Hagoolya. UMASS --Seung Hyun Kim,
Joonwon Bae, Matthew J. Misner, UMASS Seung Hyun Kim, Joonwon Bae,
Matthew J. Misner, Tom Russell Tom Russell Stanford --Marissa
Caldwell, Li-Wen Chang, H.-S. Philip Wong Stanford Marissa
Caldwell, Li-Wen Chang, H.-S. Philip Wong Eindhoven Jos Paulusse,
Bert Meijer Eindhoven Jos Paulusse, Bert Meijer
