Dr. Robert P. Meagley Intel’s Researcher in Residence Lawrence Berkeley National Laboratory

1. Beyond PFOS- Preorganized Lithographic Materials at Intel’s Molecules for Advanced Patterning Program Dr. Robert P. Meagley Intel’s Researcher in Residence Lawrence Berkeley National Laboratory MAPP http://www.intel.com/technology/techresearch/people/bios/meagley_r.htm

2. Outline • Why MAPP? • Why deploy at the Molecular Foundry? • What do we do here? • 1st 18months: Conclusions

3. Lithography Meagley, Robert P., “Sub 30nm Photoresist Design Considerations: Molecular Nanotechnology”, Future Fab International, 21, 2006

4. 65nm Node Intel Lithography Roadmap • SA Challenges: • Roughness • Resolution • Defects Nearly two billion transistors  “Montecito” 193nm litho into 32nm node then EUV DUV Molecular CDs Molecular Defects EWH 35nm EUV

5. Molecules for Advanced Patterning National Lab Accelerate discovery in nano-lithography Intel University Supplier “Technology Tetrahedron”

6. Program Structure • Capabilities • Metrology (Foundry, NCEM) • Chemical: LC/MS, MALDI, NMR • Surface: elipsometry, SEM, CFM • Lithography (ALS, Foundry, UCB) • 248nm, e-beam UCB Microlab • EUV MET, Nanowriter • Synthesis (Foundry) • Prototyping in <10g lots • 4 Fume hoods & drybox in two 500 sq. ft. labs • People • Intel Components Research Sr. Staff Scientist • 3 Post-docs one position now open (LBNL) • Contractors, assistants & visitors • Collaborations: NIST, UWI & tech transfer

7. Photoresist Structures 500nm Intrinsic ordering impacts image Several levels 50  10 nm Empirically engineered for HVM AFM reveals high levels of organization

8. Benefits of Preorganization H+ Polymer (i)  Polymer (s) PAG  H+ B- + H+ HB Base Pixel Acid Micelle/Dendrimer Oligomer Film • Catalysis fast within pixel, slow outside • Higher Eact PGs/ Higher pKa acids • Self-assembly disruption adds contrast • Diffusion control beyond PFOS Greener chemistry, enhanced performance

9. Some Prototypes

10. APPAG • Adhesion Promoting Photo Acid Generator • Pre-organizes catalyst boost signal/noise • Siloxane with pendant active species • Ultra thin films and SAMs • Building block for more complex structures • Pre-organize catalyst & switch for kinetic advantage • Base localizes catalyst for pixel discrimination Moiety placement guides proton trajectory

11. APPAG Chemistry Monomer MALDI- TOF • Tuned diffusion for CD contol • Tuned thickness with Mw control • Surface-seeking PAG • Faster photospeed

12. 1st APPAG Print Test Commercial resist applied over an underlayer The control is a commercial BARC 36 mj/cm2, 0 micron focus 40mj/cm2, 0.8 micron focus Control: square at zero focus but footed out of the focus APPAG: Square profile retained at zero and out of focus

13. Bossung plots (DUV exposure) 36mJ/cm2 250nm mask Triflate improved DUV depth of focus

14. Scissionable Quencher Backbone • Quencher integration in the polymer backbone • Pre-organize catalyst & switch for kinetic advantage • Base localizes catalyst for pixel discrimination • Pre-organize catalyst & switch for kinetic advantage • Base localizes catalyst for pixel discrimination Moiety placement guides proton trajectory

15. SQB 1st Prototype Flexible linker EUV Dose mJ/cm2 Geometric Acceleration: “Spatio-temporal Effect”

16. Rigid SQB Prototype

17. Scissionable Steroidal Dendrimer • Scissionable host made with bile acids • Pre-organized catalyst for kinetic advantage • Disrupted preorganization adds solubility • Micelle controls peripheral & interior chemistry • G0 and G1 analogs prepared • First G0 resolves 300nm • Pre-organize catalyst & switch for kinetic advantage • Base localizes catalyst for pixel discrimination Moiety placement guides proton trajectory

18. Scissionable Steroidal Dendrimer Morphology from Casting Solvent

19. H O O H H C O C H 3 3 C H 3 H O Swern O O O O TFAA H C O C H 3 H C 3 C H H C 3 O 3 3 C H • MeLi • I H O R= O(O)CCF 3 3 R I O O O H C H C 3 O O 3 C H 3 H C C H H C 3 O O 3 3 C H 3 O C H 3 H C O C H 3 3 C H 3 H O G1 Dendron & Hyperbranching

20. G1 Dendrimer extended conformation

21. 18th Month Conclusions • MAPP in Molecular Foundry “Jumpstart” • 6 months from empty room to 1st prototype • 4 designs and 18 prototypes in 1st year • Diffusion control through preorganization • APPAG steers proton with interface • SBQ steers proton with base • SDR Steers proton with polarity • Future materials needed • Pattern anticipation • Dimensional decoupling (Z from X-Y, X from Y) Diffusion control to eliminate PFOS

22. Acknowledgements • Intel: Dr. Mike Mayberry, Melissa Shell, Dr. Michael Leeson, Dr. Heidi Cao, Dr. Adam Schafer, Dr. Wang Yueh, Vani Thirumala • Molecular Foundry: Dr. Eduardo Saiz, Dr. Geeta Sharma, Dr. Shalini Sharma, Ankur Gupta, Kate Goodin, Michael Rattner, Igor Tregub • NCEM: Doreen Ah Tye & DOE* • ALS: Brian Hoef and Paul Denham • UCB Microlab team • UWI: Prof. Paul Nealey, Prof. Padma Gopalan, Dr. Insik In, Young-Hye Na • Thank you for your attention! • # DE-AC02-05CH11231

23. Backup

24. APPAG Mass Spectroscopy

25. Low level light exclusion key in 2nd step DOE in synthesis: ES MS of APPAG intermediate • Initial results inconsistent • DOE revealed “cliff” at 120 degrees RT 120 1h 120 2h 140 1h 160 1h 140 1h APPAG6

26. SBQ Mass Spectroscopy

27. 2006 Publications/Presentations • R. Meagley, S. Sharma, G. Sharma, K. Goodin, M. Rattner, “Smart Interfaces: improving pattern fidelity with the gain enhancing underlayers, APPAG”, J. Macromolecular Sci., 45(6), 2006 (invited paper, in Press) • R. Meagley “Sub 30nm photoresist design” Future fab International, Issue 26, June 2006 (invited paper) http://www.future-fab.com/documents.asp?d_ID=4005 • G. Sharma, S. Sharma, R. Meagley “Preorganization in Photoresist Architecture” 12th Wintertur Symposium on Polymers for Microelectronics May 3, 2006 (invited talk) • J.M. Roberts, R. Meagley, T.H. Fedynyshyn, R.F. Sinta, D.K. Astolfi, R.B. Goodman, and A. Cabral, Proc. SPIE 6153 (2006). • T.H. Fedynyshyn, R.F. Sinta, D.K. Astolfi, A. Cabral, J.M. Roberts, and R. Meagley, Proc. SPIE 6153 (2006).