· scft theory vs. experiment (pep-b-pee) (bates, 1994; matsen, 1996) ... interacting nanomagnet...
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www.umass.edu/chmwww.umass.edu/chm
Jim WatkinsCenter for Hierarchical ManufacturingUniversity of Massachusetts Amherst
Materials and Process Integration Challenges for the Fabrication of Nanotechnology Enabled Devices
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Nanofabrication and Integration Across Multiple Length Scales Example: Next Generation ICs
20 nm
Chip 10-2 M
Interconnect Via10-7 M
Porous ULK 10-9 M
BCP Template for Airgap10-8 M
A challenge that can only be solved by employing self-assembly
Top-down meets bottom-up
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Sectors MemoryPatternedMedia
PatternedElectrode Solar CellEnergy Self-assembled
Heterojunction
Separation/Detection
ArrayBiosensorHealth Molecular
Recognition
Bridging Manufacturing Lengths Scales Through Directed Self-Assembly and Nanopatterning
Bottom-up Top-down Integration
Nano
Computing
Micro Systems
Interconnects ChipsSelf Assembled
Templates & Pores
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Manufacturing of Nanodevices: High Level View of Overarching Challenges
Massively Parallel Generation of Well-Defined Nanostructures
Functionalization of Device Structures
Integration into Viable or Existing Process Platforms
Rapid, Cost-Effective, Defined Need
• Directed Self-Assembly• Nanoimprint and Capillary Force Lithography• Bio-assisted Assembly• Other
• 3-D Replication of Self-Assembled Templates• Deposition within Nanoscale Features• Incorporation of Nanoparticles and QDs• Other
• Si-Wafer Technology• Roll-to-Roll Processing• Insertion of one or more new nano processes
• Unique Performance Advantage = Adaptation• Application Verification
Nanofabrication Technologies
Process Technologies
Considerations for Commercialization
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Block CopolymerPatterning
Bio-AssistedAssembly
NanoimprintLithography
Structure Generation Functionalization Device Design
Nanoscale Process Platform Technologies
Integrated Multiscale Process Platform Technologies
Top-down SiWafer Technology
Continuous FeedRoll-to-RollTechnology
• Energy• Computing• Human Health
Nanoscale Deposition
3-D Replication
Functional Additives
Nano-EnabledApplications
Development withTool Suppliers
Market
CHM Nanofabrication Research Platform
Nano Scale Micro Scale Device/System Scale Product
Integration
Partners: Univ. of Puerto Rico - Rio Piedras ● Mt. Holyoke College ●Springfield Technical Community College ● Binghamton University ● UC Riverside ● TIAX LLC ● Alcatel-Lucent
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Block Copolymer Templates: Spontaneous Assembly upon Spin Coating, Complete Control of Morphology
Key Parameters: block volume fraction, f controls morphologydegree of polymerization, N controls domain sizeFlory Parameter, χ χN controls segregation
BCCSpheres
HEXCylinders
Gyroid ( )Bicontinuous Lamellae
dIa3BCCSpheres
HEXCylinders
Gyroid ( )Bicontinuous Lamellae
dIa3
Increasing f
Di-block Copolymer BCP Phase DiagramSCFT Theory vs. Experiment (PEP-b-PEE)
(Bates, 1994; Matsen, 1996)
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Hierarchical Processing
• Multi-length scale assemblies• Structural control on local and device level
S C G L G ′ C ′ S ′
Lithography Domain Alignment
PMS-PHOST BCP 248 nm ResistLi et al. Chem Mater 16, 3800 (2004)
Aligned PS-PEO cylinders Kim et al. Adv Mater 16, 226 (2004)
Nanoimprint
PS-PMMA using NILLi et al. Nano Lett. 4, 1633 (2004)
Aligned PS-PMMA Kim et al. Nature. 424, 411 (2004)
Epitaxial Assembly
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Self-Assembled Templates for Device Applications
Strongly SegregatedBCP/Surfactant Blendson Flexible Substrates
Directed Assembly ofBCPs with Long RangeOrder on Si Wafer
increase segregation strength
χN
5 nm resolutionresists and etch masks
14 Rows; 635 nm14 Rows; 635 nm
PVs, flexible electronics, displays
metaldeposition
data storage
H+ homopolymers
ion complexation
sub-micron coatingphase selective
functionalization or etch
etch contrast
H+ additives
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Integration of Self-Assembly within Process Flows?
Implementation Challenges:• Simple, rapid, cost-effective, non-disruptive process• Long-range ordering is necessary for many applications• Increase strength of segregation to decrease feature size• Low/no defect tolerance• Commodity scale availability for ordered systems• Patterned media• Metrology
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Current requirement for magnetic data dots for BPM:Size and position distributions <5% per data sector
14 Rows; 635 nm
Exploiting Cooperativity Across Length Scales:Hierarchical Processing Using Block Copolymers
S C G LS C G L
Evaluation of self assembly for ordered magnetic media
Block Copolymers: Jitter of 4.5% !!With Oleg Myrasov Seagate Technologies
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Recent Progress: Vertical Orientation Via “Zone Refinement”and Near Perfect Lateral Ordering Through Solvent Annealing
10 μm x 10 μm
As-spun
(PS-b-P4VP: 47.6k-20.9k)Solvent annealing
SFM
SFM
Voronoi
Voronoi
2 µm x 2 µm
2 µm x 2 µm
substrate
SolventEvaporation
DISORDERED ORDERED
r
φs
Ordering Front
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Hierarchical Self-Assembly: Clusters in Wells
Interacting Nanomagnet Cluster — Overcomes R/W lateral resolutionMULTISTATE DATA STORAGE
8 stable magnetic states
LLGSimulation
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4-State Data Storage Element
MFM images of a 3-nanomagnet cobalt cluster
"0" "1" "2" "3"
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Self-Assembled Templates for Device Applications
Strongly SegregatedBCP/Surfactant Blendson Flexible Substrates
Directed Assembly ofBCPs with Long RangeOrder on Si Wafer
increase segregation strength
χN
5 nm resolutionresists and etch masks
14 Rows; 635 nm14 Rows; 635 nm
PVs, flexible electronics, displays
metaldeposition
data storage
H+ homopolymers
ion complexation
sub-micron coatingphase selective
functionalization or etch
etch contrast
H+ additives
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Bulk-Scale Well-Ordered Block Copolymer Materials?
• High degrees of order generally require high purity, low polydispersity• Commodity block copolymers are polydisperse, contain impurities
– e.g. Pluronic surfactants• Commercially available and inexpensive• Weakly segregated domains, PDI = 1.2, diblock impurities
[-CH2-CH2-O]m -[CH2-CH(CH3)-O]n [-CH2-CH2-O]m
Polymer Total MW (g/mol)
fPEO χN(calc.)
χN* (critical)
Est. ODT (K)*
L92 3,450 0.2 5.75 40 113.5
P105 6500 0.48 10.5 19 274
F108 14,600 0.8 20.29 32 337.5
E70(dP)31E70 8400 0.8 12.5 32 227
• Pluronics do not exhibit phase segregation in the meltLow χPEO-PPO: χ(T) = -0.122+66.8/T;χPEO-PPO @ 80 °C = 0.066-0.068;(Ryan, Booth, and coworkers, Phys. Chem. Chem. Phys. 2000, 2, 1503-7.)
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Strengthening Phase Segregation via Segment Specific Interactions: Well-Ordered Materials by The Barrel
Impact: Will enable use of BCP templating in low cost applications (roll to roll, extrusion)Increases in χN will reduce feature size
We find blending with homopolymers that H+ bond to the majority PEO block yields exceptionally well-ordered materials by increasing segregation
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0
0.02
0.04
0.06
0.08
0.1
NONEPAA (0
.16)
PAA (0.69
)PAMPS (0
.34)
PSSA (0.33
)PHS (0
.39)
q* (A)FWHM (A -̂1)
Strengthening Phase Segregation via Segment Specific Interactions: Stable Functional Templates
SANS dF68/ 40% homopolymer Evidence of Enhanced Segregation
Broad Class of BehaviorCH2
CHn
COHO
CH2CH
n
COHO
CH2CH
n
OH
CH2CH
n
OH
S OO
OH
n
S OO
OH
n
Introduction of Functional GroupsFacilitates Modification
TEM of Cobalt in L92-PAA blend
dF68 dF68/PAA
Impact: functional self-assembled templates that can be coated at high rate
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35 nm rods 60 nm rods 20 nm rods 40 nm rods
Nanorods in trenches Nanorods in cylinders
=HS OOH
9 4
Functionalized CdSe Nanorods:Induce Compatibility and Corralling in
Polymer Templates
Emrick and Russell
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Precursor in Humidified CO2
• High fidelity preservation of morphology• Easily integrated with existing technologies• Rapid, robust, scalable
S C B L
• Phase-selective chemistries• Catalyst localization
3-D Template Replication Using Phase-Selective Chemistries
Porous silica
Porous carbon
Impact: Transfer hierarchical structures easily obtained in BCPs into other materials
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k< 2.2 demonstrated Rapid process times, 1st generation survives CMPLow stress, high crack thresholdFirst principles molecular dynamics simulationsproviding structure-property guidance
First generation films exhibit excellent performance for ULK
Mesoporous Silicate (ULK) Films Prepared in CO2
20 nm
Leveraged with SRC Support
Two Important Observations: Small pores are accessible via template blends
– increase in χn reduces feature size– 3 nm is inaccessible via typical BCPs
Ability to decouple alkoxide condensation from template assembly will enable complete definition of desired hierarchical architecture in a suitable template
TEM Showing 3 nm Pores
MD Simulation Relates Structure to Mechanical Properties
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Micro-Patterned Mesoporous Silica FilmsSimultaneous Domain (nanoscale) and Device (microscale) Control:
Chemical amplification and Silica Condensation in PS-b-PtBocSt Films
Template removal
UV exposure
Post-exposure bake &Silica infusion
PHOST
Patterned silica film
Photo acid generator
Generated Acid
PtBocStPS
PS
TEOS in SC CO2
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Patterned Mesoporous Silica Films from PBOCStyrene Films
Good pattern replication with sharp boundaries.Device level features down to few microns in size
+ PAG(H+)
1. UV exposure
2. Post exposure Bake (PEB)
+
PtbocStHydrophobic
PHOSTHydrophilic Regeneration of acid
+ PAG(H+)
1. UV exposure
2. Post exposure Bake (PEB)
+
PtbocStHydrophobic
PHOSTHydrophilic Regeneration of acid
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~ 4 µm~ 4 µm
~ 3.5 µm~ 3.5 µm~ 3.5 µm
Direct Pattering of Silica Films via Hybrid Processing: AFM Images
Good pattern replicationDevice level features below 100 nm!No etching: significant process advantageTemplate optimization with partners underway
Simple Contact Mask LithographyPtbocSt and PtbMA Templates
Off-the-Line 193 Resist from Partner(Acrylate-based, first attempt: No optimization)
Impact: Potential for streamlined integration of ULKs and cost savings via process simplification
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Viral Capsids as Nanomaterials
Nano Letters 2006, 6, 611-616
Biocompatible monolayer provides >95% efficiency in assembly of Brome Mosaic Virus (BMV) Encapsidated particles self-assemble into
ordered structures.
Biology in the Service of Materials: Bio-Assembly
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Ordered 2-D and 3-D DNA-BCP Nanostructures
Repeating DNA patterns used to create simple objects (e.g., tetrahedra)
Electrostatic interactions allow for site-specific registration of DNA objects with BCP films
Subsequent metallization using low temperature SCF approaches planned
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Opportunities• Self assembly can be integrated with top down processing
- precision assembly on Si wafer platforms- high rate, low cost assembly for roll-roll processing
• Elements accessible from self assembly offer both new possibilities and constraints for device design
• Hybrid processes can offer performance and economic advantages
• Biological elements combined with synthetic self assembly platforms offer new versatility
-deterministic assembly on surfaces may be required
• Functionalization and metrology remain challenges