NSF Nanoscale Science and Engineering Center for High-rate Nanomanufacturing

1. NSF Nanoscale Science and Engineering Center for High-rate Nanomanufacturing Thrust 3: Testbeds Nick McGruer Director: Ahmed Busnaina, NEU Deputy 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

2. CHN Path to Nanomanufacturing Thrust 2: High-rate Assembly and Transfer NEU; UML; UNH Thrust 4: Societal ImplicationsNEU; UML Education & Outreach NEU; UML; UNH Thrust 1: Manufacture Nanotemplates and Nanotubes NEU; UNH Thrust 3: Testbeds Memory Device and Biosensor NEU; UML; UNH Nanotube Devices Testbed BiosensorsTestbed Alignment Processes Reliability andDefect Control Developing Testbeds and Applications

3. NSF Center for High-rate NanomanufacturingApplication Road Map

4. Thrust 3: Testbeds, Memory Device and Biosensor PIs: Ahmed Busnaina, Nick McGruer, George Adams, NEU Post Docs: Siva Somu, Nam Goo Cha, NEU. Students: Taehoon Kim, Anup Sing, Suchit Shah, NEU. Nanotube Devices Testbed PIs: Joey Mead, Carol Barry, Susan Braunhut, Ken Marx, Sandy McDonald, UML, Ahmed Busnaina, NEU. Post Docs:, Lisa Clarizia, UML. Students: Vikram Shankar, UML. BiosensorsTestbeds Alignment Processes PIs: Ahmed Busnaina, Nick McGruer, NEU, Jim Whitten, UML, Howard Mayne, UNH. Students: Jose Medina, Jagdeep Singh, UML. Reliability andDefect Control PIs: Ahmed Busnaina, Nick McGruer, George Adams, NEU. Students: Juan Aceros, Peter Ryan, NEU. Developing Testbeds and Applications PIs: Sanjeev Mukerjee, Nick McGruer, Ahmed Busnaina, Mehmet Dokmeci, Jung Joon Jung, NEU, Glen Miller, UNH, Joey Mead, Carol Barry, UML

5. What are the Critical Barriers to Nanomanufacturing? • 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.

6. Two Established Proof of Concept Testbeds • Chosen to verify CHN- Developed manufacturing processes. • Easy to measure to validate functionality. • Strong industry partnership for product realization. Nanotube Memory Device Partner: Nantero first to make memory devices using nanotubes • Biosensor Partner: Triton Systems developed antibody attachment for medical applications • Properties:increased sensitivity, smaller sample size, detection of multiple antigens with one device, small/low cost. • Properties:nonvolatile, high speed programming at <3ns, lifetime goal >1015 cycles, resistant to heat, cold, magnetism, vibration, and radiation.

7. Four Examples of Carbon Nanotube Switches MWNT Mechanical Switch Jang et al., Appl. Phys. Lett. (2005) 87, 163114. 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. Self-assembled switches based on electroactuated multiwalled nanotubesE. Dujardin,a V. Derycke,b M. F. Goffman, R. Lefèvre, and J. P. Bourgoin Applied Physics Letters 87, 193107 2005

8. High Density Memory Chip Testbed Current Nantero process • Uses conventional optical lithography to pattern carbon nanotube films • Switches are made from belts of nanotubes ON state OFF state • CHN Nanomanufacturing • Processes: • Nanotemplates will enable aligned CNT. • Near Term, smaller linewidth, better process control. • Ultimately, single CNT switches. Electrodes (~100nm with 300 nm period) (Nantero, 2004)

9. Template Transfer Technology Validation in Memory Device Testbed CNTs on trenches form memory elements. Testbeds: Memory Devices Testbeds: Memory Devices and Biosensor Assemble and Transfer Nanoelements Carbon nanotubes assembled from solution Manufacture Nanotemplates and Nanotubes

10. 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.

11. Directed Assembly of a Single SWCNT by Dielectrophoresis

12. 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

13. ELISA (Enzyme-Linked ImmunoSorbent Assay), Background Add Sample Wash Capture Antibody Bind Antigen Add Signal Conjugate Antigen binding sites Elisa analysis of a serum sample with breast cancer. Source: Richard Zangar, Nature Adsorb primary antibody onto a solid substrate Bind antigen (biomarker for specific disease) to antibody Add labeled detection antibody Detection Detection of fluorescence or color change of substrate

14. Biosensor; State of the Art Elisa analysis of a serum sample with breast cancer. Source: Richard Zangar, Nature • 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 F. Patolsky and C.M. Lieber, "Nanowire nanosensors," Materials Today, 8, 20-28 (2005)

15. Increase Performance of Antibody-Based Sensors Spacing too wide for maximum sensitivity Spacing too close for antigen detection • Opportunity: • Random orientation and spacing of antibodies. • Want to control: • Orientation of antibodies (Functional antibodies estimated to be : 10-20%) • Spacing of antibodies. • 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. • 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.

16. Orientation FAB FC • Ratio of Oriented (Fab) to disOriented (Fc) response was much higher for the CHN system. RATIO POLYMER CHN

17. 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

18. 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.

19. Reliability, Accelerated Test, Properties • 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

20. MEMS Nanoscale Characterization and Reliability Testbed, Introduction • 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).

21. MEMS Testbed for Accelerated Testand Properties Measurement • 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.

22. MEMS Nanoscale Characterization and Reliability Testbed, Nano Pull Test Currently characterizing electrospun fibers from UML.

23. MEMS Nanoscale Characterization and Reliability Testbed, Hot Plate with Nanowire Au, Ru, and RuO2 nanowires tested, currently testing CNT bundles.

24. AFM Measurement of CNT-Surface Interaction (in support of assembly, transfer and CNT switches). • What: Development of techniques for measurement of interactions between functionalized nanotubes and functionalized surfaces. • Purpose: Process control for single nanotube switch process. F/d On neighboring Substrate F/d On Suspended CNT RMS and A-B Data Plotted for a 100 nm Z-Piezo Displacement Below the Substrate

25. Summary and Goal • Generally Applicable Tools Available Now for: • Measurements of Reliability of Nanoelements, Contacts, and Systems. • Accelerated Test of Nanoelements, Contacts, and Systems. • 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.

26. SiO2 Si P-type SWNT Assembly N-type SWNT Assembly P type P type N type N type • 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. Low Cost, High Power and Energy Density Secondary Storage Batteries High rate 2D templates for Microbatteries SWNTs Assembled within polymer 260 nm trenches over 100m long in 60 Sec.

27. Si/SiO2 Substrate Co Seed Catalyst Patterning SWNT CVD Growth 3D templates for Microbatteries Grown SWNT pillars Jung, NEU SWNT network grown between SiO2 nano pillars. Jung, NEU

28. Lightweight Structural Materials with Integrated Wiring, Thermal Management, and EMI Shielding assembly transfer • Controlled orientation of CNTs • Patterned conducting elements (thermal and electrical) • Embed in polymeric matrix Reduced time to implement since process has been developed

29. Lightweight Structural Materials Process can be advanced to produce large sheets Widths: 3-6 feet Rates: 60  48,000 feet per hour Polymer film Patterned surface Template roller with nano or micro patterns Carbon nanotubes CNT supply Lightweight structural materials

30. 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

31. Thermal Management • Nanoparticles and carbon nanotubes • Greater thermal conductivity than polymers

32. 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