Beyond PFOS- Preorganized Lithographic Materials at Intel’s

Molecules for Advanced Patterning Program

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

MAPPMAPPhttp://www.intel.com/technology/techresearch/people/bios/meagley_r.htm

Outline

•Why MAPP?

•Why deploy at the Molecular Foundry?

• What do we do here?

• 1st 18months: Conclusions

Lithography

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

Nearly two billion transistors “Montecito”193nm litho into 32nm node then EUV

Intel Lithography Roadmap

SA Challenges:SA Challenges:•RoughnessRoughness•ResolutionResolution•DefectsDefects

MolecularMolecularDefectsDefects

MolecularMolecularCDsCDs

EWH35nm

DUV

EUV

65nm Node

Accelerate discovery in nano-lithography

IntelIntel

National Lab

SupplierUniversity

“Technology Tetrahedron”

Molecules for Advanced Patterning

• 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

Program Structure

500nm

Photoresist Structures

AFM reveals high levels of organization

Intrinsic ordering impacts imageSeveral levels 50 10 nmEmpirically engineered for HVM

H+ Polymer (i) Polymer (s) PAG H+ B- + H+ HB

Base

AcidPixel Micelle/Dendrimer Oligomer Film• Catalysis fast within pixel, slow outside• Higher Eact PGs/ Higher pKa acids• Self-assembly disruption adds contrast• Diffusion control beyond PFOSPFOS

Benefits of Preorganization

Greener chemistry, enhanced performance

Some Prototypes

Class Types Result

APPAGLong & Short Diffusion helps

DOF & profile248nm, 193, EUV, e-

beam

Scissionable Steroidal

Dendrimer

Scissionable Host for PAG Guest

6 kinds of G0 madeG1 made in June

G0 gave <5mJ/cm**2 EUV working on

increased temperature resistance

Scissionable Quencher Backbone

Preorganized quencher directs acid to protection

6 copolymers

10mJ/cm**2 EUV working on increased

temperature resistance

Nano-composite C, Si filler

Diamond nano-powder needs better dispersion

Advanced Developer proprietary

Fast photospeed, low PEB, short diffusion,

large margin

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-organiz e cata lyst & s witch for k inetic a dvantage

• Bas e loca lizes c atalys t for pixel discrimination

Moiety placement guides proton trajectory

Corrected profile

Sloped profile

H+H+

H+

H+

H+

H+H+H+

H+H+

H+

H+

H+H+

APPAG Chemistry

Monomer MALDI- TOF

• Tuned diffusion for CD contol• Tuned thickness with Mw control• Surface-seeking PAG• Faster photospeed

Control: square at zero focus but footed out of the focus

APPAG: Square profile retained at zero and out of focus

36 mj/cm2, 0 micron focus 40mj/cm2, 0.8 micron focus

1st APPAG Print Test

Commercial resist applied over an underlayerThe control is a commercial BARC

-1.5 -0.9 -0.26 +0.38 +1Defocus,

300

238

175

115

50

CD, nm

defocus 0

APPAG9

APPAG6

Control

-1.5 -0.9 -0.26 +0.38 +1Defocus,

300

238

175

115

50

CD, nm

defocus 0

APPAG9

APPAG6

Control

36mJ/cm2

250nm mask

Triflate improved DUV depth of focus

Bossung plots (DUV exposure)

Scissionable Quencher Backbone

• Quencher integration in the polymer backbone

• Pre-organize catalyst & switch for kinetic advantage

• Base localizes catalyst for pixel discrimination

• Pre-organiz e cata lyst & s witch for k inetic a dvantage

• Bas e loca lizes c atalys t for pixel discrimination

Moiety placement guides proton trajectory

SQB 1st Prototype

Flexible linker

EUV Dose mJ/cm2

Geometric Acceleration: “Spatio-temporal Effect”

Rigid SQB Prototype

Scissionable Steroidal Dendrimer

Moiety placement guides proton trajectory

Morphology from Casting Solvent

Scissionable Steroidal Dendrimer

G1 Dendron & Hyperbranching

OH

CH3

O

OH

CH3CH3

OH

Swern

O

CH3

O

OH

CH3CH3

O

TFAAO

CH3

O

R

CH3CH3

O

R= O(O)CCF3

I

1) MeLi2) I

O

CH3

O

O

CH3CH3

O

O

CH3

O CH3CH3

O

CH3

O

OH

CH3CH3

CH3

O

CH3

G1 Dendrimer

extended conformation

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

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

Backup

APPAG Mass Spectroscopy

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

• Low level light exclusion key in 2nd step

SBQ Mass Spectroscopy

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).