NSF Nanoscale Science and Engineering Center for High-rate Nanomanufacturing

Director: Ahmed Busnaina, NEUDeputy Director: Joey Mead, UML, Associate Directors: Carol Barry, UML; Nick McGruer, NEU;

Glen Miller, UNH; Jacqueline Isaacs, NEU, Group Leader: David Tomanek, MSU

Collaboration and Outreach: Museum of Science-Boston, City College of New York, Hampton Univ., Rice Univ., Hanyang Univ., Korean Center for Nanoscale Mechatronics and Manufacturing (CNMM),

University of Hyogo, Japan

Thrust 3: TestbedsThrust 3: TestbedsNick McGruerNick McGruer

Thrust 3: Testbeds Memory Deviceand Biosensor

NEU; UML; UNH

Thrust 1: Manufacture Nanotemplates

and NanotubesNEU; UNH

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Thrust 2:High-rate

Assembly and TransferNEU; UML; UNH

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CHN Path to Nanomanufacturing

Biosensors Testbed

Nanotube Devices Testbed

Reliability andDefect Control

Alignment Processes

Developing Testbedsand Applications

NSF Center for High-rate NanomanufacturingApplication Road Map

Thrust 3: Testbeds, Memory Device and Biosensor

PIs: Joey Mead, Carol Barry, Susan Braunhut, Ken Marx, Sandy McDonald, UML, Ahmed Busnaina, NEU.

Post Docs:, Lisa Clarizia, UML.Students: Vikram Shankar, UML.

PIs: Ahmed Busnaina, Nick McGruer, George Adams, NEUPost Docs: Siva Somu, Nam Goo Cha, NEU.Students: Taehoon Kim, Anup Sing, Suchit Shah, NEU.

PIs: Ahmed Busnaina, Nick McGruer, NEU, Jim Whitten, UML, Howard Mayne, UNH.

Students: Jose Medina, Jagdeep Singh, UML.

PIs: Ahmed Busnaina, Nick McGruer, George Adams, NEU.Students: Juan Aceros, Peter Ryan, NEU.

Biosensors Testbeds

Nanotube Devices Testbed

Reliability andDefect Control

Alignment Processes

Developing Testbedsand Applications PIs: Sanjeev Mukerjee, Nick McGruer, Ahmed Busnaina,

Mehmet Dokmeci, Jung Joon Jung, NEU, Glen Miller, UNH, Joey Mead, Carol Barry, UML

Barrier 2. How can we scale up assembly processes in a continuous or high rate manner? Demonstration of assembly processes; scale-up; technology transfer.

Barrier 3. How can we test for reliability in nanoelemnts and connections? How can we efficiently detect and remove defects? MEMS Testbed for accelerated test of nanoelements. Collaboration with the Center for Microcontamination Control on removal of

nanoscale defects.

Barrier 4. Do nanoproducts and processes require new economic, environmental, and ethical/regulatory assessment and new socially-accepted values? Testbed process can be case studies for environmental, economic, and

regulatory needs.

What are the Critical Barriers to Nanomanufacturing?

BiosensorPartner: Triton Systems developed antibody attachment for medical applications

Properties: increased sensitivity, smaller sample size, detection of multiple antigens with one device, small/low cost.

Nanotube Memory DevicePartner: Nantero first to make memory devices using nanotubes

Chosen to verify CHN- Developed manufacturing processes. Easy to measure to validate functionality. Strong industry partnership for product realization.

Two Established Proof of Concept Testbeds

Properties: nonvolatile, high speed programming at <3ns, lifetime goal >1015 cycles, resistant to heat, cold, magnetism, vibration, and radiation.

Four Examples of Carbon Nanotube Switches

Carbon Nanotube Non-Volatile

Memory Device, Ward, J.W.; Meinhold, M.; Segal, B.M.; Berg, J.; Sen, R.; Sivarajan, R.; Brock, D.K.; Rueckes, T. IEEE, 2004, 34-38.

MWNT Mechanical SwitchJang et al., Appl. Phys. Lett. (2005) 87, 163114.

Self-assembled switches based on electroactuated multiwalled nanotubes E. Dujardin,a V. Derycke,b M. F. Goffman, R. Lefèvre, and J. P. Bourgoin Applied Physics Letters 87, 193107 2005

High Density Memory Chip Testbed

Electrodes(~100nm

with 300 nm period)

ON state OFF state

CHN Nanomanufacturing Processes:•Nanotemplates will enable aligned CNT.

•Near Term, smaller linewidth, better process control.

•Ultimately, single CNT switches.

Current Nantero process Uses conventional optical lithography to pattern carbon nanotube films Switches are made from belts of nanotubes

(Nantero, 2004)

Template Transfer Technology Validation in Memory Device Testbed

Testbeds: Memory Devices

and Biosensor

Manufacture Nanotemplates and

Nanotubes

CNTs on trenches

form memory

elements.

Testbeds: Memory Devices

Carbon nanotubes assembled from solution

Assemble and Transfer Nanoelements

Type II CHN Nanotube Switch for Non-Volatile Memory

Schematic of state I and II.

• Type II Switch has two symmetric non-volatile states.• Simple process.• CNTs assembled directly on chip using

dielectrophoresis or using template transfer.• Measurements in progress.• CNT/Surface interaction critical, measurements in

progress.

Directed Assembly of a Single SWCNT by Dielectrophoresis

SWNT Memory Testbed Status and Plan

• Why Important?– We need new manufacturing methods to scale beyond CMOS (to approach

terabytes/cm2 in memory density for example).– CHN templates will reduce current line width by 10X (10 nm line width) in

the initial phase.– Developing manufacturing processes for manipulating

nanotubes/nanoelements. Can be applied to FETs, molecular switches.

• Current Status– Developing templated and template-less SWNT assembly techniques.– Preparing silicon-based and polymer-based templates to develop transfer

processes.– Fabricating Nantero-style switches and switches

with a symmetrical two-state design.

• Transition Plan– In 2009 will have large scale directed assembly

of SWNT over 4” wafers– Technology transfer anticipated by 2012

Adsorb primary antibody onto a solid substrate

Antigen binding

sites

Bind antigen (biomarker for specific disease) to antibody

Add labeled detection antibody Detection of

fluorescence or color change of substrate

ELISA (Enzyme-Linked ImmunoSorbent Assay), Background

Elisa analysis of a serum sample with breast cancer.

Source: Richard Zangar, Nature

Biosensor; State of the Art

• Commercial ELISA systems• Cantilevers for detection

– M. Calleja et al, IMM-Centro Nacional de Microelectronias, Tres Cantos, Spain

– V. Dauksaite et al, University of Aarhus, Aarhus, Denmark

• Nanowire sensors– Antibodies are not patterned (immobilized), so

maximum sensitivity is not attained

Cantilevers are coated with antibodies to PSA, When PSA binds to the antibodies, the cantilever is deflected, Mujumdar, UC BERKELEY

Elisa analysis of a serum sample with breast cancer.

Source: Richard Zangar, Nature

F. Patolsky and C.M. Lieber, "Nanowire nanosensors," Materials Today, 8, 20-28 (2005)

Increase Performance of Antibody-Based Sensors

Spacing too close for antigen detection

Spacing too wide for maximum sensitivity

Controlled orientation: Can increase sensitivity by 5-10x. Templates not required.

Method 1: Chemical attachment May disrupt antibody activity. Must evaluate for a specific

antibody. Method 2: Protein G based attachment.

Opportunity:• Random orientation and spacing of

antibodies.• Want to control:

•Orientation of antibodies (Functional antibodies estimated to be : 10-20%)•Spacing of antibodies.

Controlled spacing:Can increase sensitivity by 5-10x?Less non-specific binding.Use templates to pattern polymer

blends.High-rate, high-volume process.Wide choice of polymers.

Fab to Fc Response Ratios

0

2

4

6

8

UHB HB MB PMMA

•Ratio of Oriented (Fab) to disOriented (Fc) response was much higher for the CHN system.

POLYMER

RA

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CHN

FAB

FC

Orientation

Keck Nano Bio Chip

Biosensor Goals– Simultaneous measurement of multiple biomarkers with one device

– Very small size (can be as small as 100 µm x 100 µm)

– Can be made of all biocompatible material

– Low cost

– Future development will lead to a device where drugs are released based on the detected antigen.

– In-vivo measurement

– No issues with sample collection and storage

BioSensor Status, Plan and Goals

• Why Important?– CHN templates will improve sensitivity by 10-100X and provide selectivity

not available now by improving both antibody orientation and spacing.– Potential for physically smaller, less expensive arrays with more

sensitivity and functionality. (Detect multiple antibodies/diseases in one test, for example.)

• Current Status– Developed oriented attachment approaches

for antibodies on candidate components of polymer blends.

– Assembly of polymer blends using templates.

• Biosensor Goals– Demonstrate high-rate assembly of antibody selective polymer blends. – Demonstrate selective antibody attachment to one component of a

template-assembled polymer blend.– Demonstrate control of antibody spacing with appropriate assembled

polymer blend pattern.

Reliability, Accelerated Test, Properties

SiO2 (2um)

Si Substrate

Si (2um)

Si Contacts

SiO2

Nanowire Contacts

N an ow ire

• Monitor reliability of materials, interfaces, and systems to ensure manufacturing readiness.

– Changes in material or contact properties with environmental exposure, stress, temperature …

• Accelerated testing for reduced manufacturing risk.

– Rapid mechanical, electrical, and thermal cycling with measurement capability.

– Example: MEMS devices to rapidly cycle strain or temperature while measuring resistance and imaging in SEM or STM. UHV compatible.

• Nanoscale material, contact, and interface property monitoring.

– Example: Measure adherance force and friction between functionalized nanoelements and functionalized substrates.

– Example: Measure Young’s modulus and yield strength of nanoelements.

MEMS Devices for Accelerated Test

Interaction of AFM Cantilever with Suspended Nanotube

MEMS Nanoscale Characterization and Reliability Testbed, Introduction

SiO2 (2um)

Si Substrate

Si (2um)

Si Contacts

SiO2

Nanowire Contacts

N an ow ire •Considerable work on MEMS resonators – properties of the resonator itself:

•C. L. Muhlstein, S. B. Brown, R. O. Ritchie, High-Cycle fatigue of Single –Crystal Silicon Thin Films, J. MEMS, 10, 4 (2001) pp. 593-600.

•Work on MEMS material properties, much less quantative work on properties/reliability of nanoscale structures or interfaces.

•M. A. Haque, M. T. A. Saif, “Mechanical Behavior of 30-50 nm thick Aluminum Films Under Uniaxial Tension”, Scripta Mat. pp 863, Vol 47 (2002).

•T. Yi, C. J. Kim, "Measurement of Mechanical Properties for MEMS Materials", Meas. Sci. Technol., pp. 706-716, Vol 10, (1999).

•M. T. A. Saif, N. C. MacDonald, “Measurement of Forces and Spring Constants of Microinstruments”, Rev. Scien. Inst. pp 1410, Vol 69, 3 (1998).

•M. Yu, B. S. Files, S. Arepalli, R. S. Ruoff, “Tensile Loading of Ropes of Single Wall Carbon Nanotubes and their Mechanical Properties”, Phys. Rev. Lett. pp 5552, Vol 84, 24 (2000).

•A. V. Desai, M. A. Haque, “Test Bed for Mechanical Characterization of Nanowires”, JNN Proc. IMechE. Part N. pp 57-65, Vol 219, N2 (2006).

MEMS Testbed for Accelerated Testand Properties Measurement

Test Devices

Tensile Test

Bend Test

Horizontal Resonator

MicroHotPlate

Angular Resonator

Test Devices

Tensile Test

Bend Test

Horizontal Resonator

MicroHotPlate

Angular Resonator

Innovative MEMS devices characterize nanowires (also nanotubes, nanorods and nanofibers) and conduct accelerated lifetime testing allowing rapid mechanical, electrical, and thermal cycling which can be combined with AFM/SEM/UHV SPM observation.

Suitable for remote testing: Space or radiation environments. Small, lightweight, low-power.

MEMS Nanoscale Characterization and Reliability Testbed, Nano Pull Test

Currently characterizing electrospun fibers from UML.

MEMS Nanoscale Characterization and Reliability Testbed, Hot Plate with Nanowire

Au, Ru, and RuO2

nanowires tested,

currently testing

CNT bundles.

AFM Measurement of CNT-Surface Interaction (in support of assembly, transfer and CNT switches).

RMS and A-B Data Plotted for a 100 nm Z-Piezo Displacement Below the Substrate

F/d On Suspended CNT

F/d On neighboring Substrate

• What: Development of techniques for measurement of interactions between functionalized nanotubes and functionalized surfaces.

• Purpose: Process control for single nanotube switch process.

Summary and Goal

• Generally Applicable Tools Available Now for:

1. Measurements of Reliability of Nanoelements, Contacts, and Systems.

2. Accelerated Test of Nanoelements, Contacts, and Systems. 3. Measurements of Properties of Nanoscale Elements and

Interactions between Elements.

• These tools will help to ensure manufacturing readiness and will help to reduce the time for technology transition to manufacturing.

Low Cost, High Power and Energy Density Low Cost, High Power and Energy Density Secondary Storage BatteriesSecondary Storage Batteries

SWNTs Assembled within polymer 260 nm trenches over 100long in 60 Sec.

P-type SWNT Assembly

Si

N-type SWNT Assembly

SiO2

N typeP type N type P type

High rate 2D templates for Microbatteries

•Sanjeev Mukerjee, Professor, Dept. of Chemistry and Chemical BiologyDirector, Energy Research Center, Northeastern University

•Collaborate with CHN to develop unique micro-arrays for 2-D and 3-D batteries based on Li-ion chemistry. 3-D designs will have up to 350 times higher energy and power density as compared to the conventional designs.

3D templates for Microbatteries

Grown SWNT pillars

Jung, NEU

SWNT network grown between

SiO2 nano pillars.Jung, NEU

Si/SiO2 Substrate

SWNT

Co

Seed Catalyst Patterning

CVD Growth

Lightweight Structural Materials with Integrated Wiring, Thermal Management, and EMI Shielding

• Controlled orientation of CNTs • Patterned conducting elements (thermal and electrical)• Embed in polymeric matrix

assembly transfer

Reduced time to implement since process has been developed

Lightweight Structural Materials

Process can be advanced to produce large sheets• Widths: 3-6 feet• Rates: 60 48,000 feet per hour

Lightweight structural materials

Carbon nanotubes

Template roller withnano or micro patterns

Patterned surfacePolymer film

CNT supply

Lightweight Structural Materials

Nanocomposites (e.g. carbon nanotubes, nanowhiskers, etc.)• Compared to conventional reinforcements

40X greater strength to weight ratio• Lighter weight and lower cost

MaterialModulus,

GPaStrength,

GPaDensity,

g/cm3

SWNT 1054 150 1.40

MWNT 1200 150 2.60

Glass fiber 87 4.6 2.50

Carbon fiber 228 3.8 1.80

Kevlar 186 3.6 ---

Steel 208 1.0 7.80

Thermal Management

Nanoparticles and carbon nanotubes• Greater thermal conductivity than polymers

Material Thermal Conductivity, W/m-K

Density,g/cm3

CNT 2000 1.4

Silver 418 10.5

Copper 386 8.95

Gold 143 2.8

Silica 1.40 2.2

Kapton (PI) 0.37 1.5

Summary, Lightweight Multifunctional Materials

• CHN provides manufacturing ready processes for light-weight, flexible materials with– High strength

• 40X greater strength-to-weight ratio– Tailored thermal management

• Thermal conductivity at < 10% particle loading• Placement of thermal management layers or wires

where required– Multiple functionalities

• Strength and thermal management• Also, internal wires, EMI shielding, and stealth

capabilities