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Craig Hawker of UCSB: Commercial Applications of Polymer as Nanomaterials
- 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 –αvβ3 αvβ5 at surface –αvβ3 αvβ5 Target platlets --αIIvβ3 Target platlets αIIvβ3
- 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
- 11. Molecular Weight Results GPC (DMF) Mn 5kDa - PEG PDI (kDa) 5kDa - PEG-Star/EGDA Star / EGDA 690 1.18 Star / DVB 750 1.19 5kDa - PEG-Star/DVB Arm-17kDa 17.0 1.08 5kDa - PEG-Arm 10 20 30 40 [min] Mn 2kDa - PEG PDI (kDa) 2kDa - PEG-Star/EGDA Star / EGDA 330 1.20 2kDa - PEG-Star/DVB Star / DVB 390 1.19 2kDa - PEG-Arm Arm-11kDa 113 1.07 10 20 30 40 [min]
- 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 β + 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 β+ (positron, PET imaging) and β- (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
- 24. Effects of PEG length on BioDistribution 100 5kDa PEG stars 5kDa PEG stars 80 % ID/organ 60 2kDa PEG stars 2kDa PEG stars 40 1kDa PEG stars 1kDa PEG stars 20 0 BLOOD 0 10 20 30 40 50 time (h) * 5-10 kDa PEG * 5-10 kDa PEG 40 * min. 20 arms * min. 20 arms * max. Mw of 1066 * max. Mw of 10 % ID/organ 30 20 10 0 LIVER 0 10 20 30 40 50 time (h)
- 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 – αvβ3 at surface – αvβ3
- 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
- 28. Synthesis of Nanoparticles Synthesis of Nanoparticles PEG: 5kDa PEG: 5kDa Orthogonal Orthogonal Latent Latent Functionalities Functionalities 120oC Mn = 18 kDa; PDI = 1.10 Mn = 18 kDa; PDI = 1.10 Arm copolymer
- 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 α vβ 3 Competitive Binding Assay Binding affinity for αvvβ3(IC50): 6.4 nM Binding affinity for α β3 (IC50): 6.4 nM 100 % Vitronectin Activity 75 Affinity for αvvβ5(IC50) > 10,000 nM Affinity for α β5 (IC50) > 10,000 nM 50 25 No targeting groups --Affinity for No targeting groups Affinity for αvvβ3and αvvβ5(IC50) > 15,000 nM α β3 and α β5 (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
- 40. Block Copolymers Block Copolymers PMMA Technologically Technologically Synthetic Synthetic Important Important PS Challenge Challenge phase morphology depends on relative polymer-block chain lengths phase morphology depends on relative polymer-block chain lengths spheres lamellae lamellae inverse-spheres inverse-spheres spheres cylinders cylinders inverse-cylinders inverse-cylinders
- 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 hν hν 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
- 64. PEO-PMMA-PSt triblock copolymer PEO-PMMA-PSt triblock copolymer PS PEO PMMA Different Morphologies
- 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
- 70. Regularity Regularity Current Photolithographic- ca. 50-100 nm Decrease Size/Maintain Regularity Decrease Size/Maintain Regularity Storage Applications, Microelectronics, Photovolatics Storage Applications, Microelectronics, Photovolatics
- 71. Market leader in Holographic Storage Market leader in Holographic Storage Holographic drive Holographic disc (tapestry™300r) 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 hν 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.
- 75. Performance Comparison Performance Comparison 50 60 50 diffraction efficiency (%) 40 diffraction efficiency (%) 40 30 407 OFF 30 20 407 ON 20 Inphase UCSB 10 10 120 sec , 42% 40 sec , 55% 0 0 0 50 100 150 200 -10 0 10 20 30 40 50 60 70 80 90 100 time (sec) time (sec) *** Holographic Speed and Efficiency is comparable
- 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