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Micro and Nanoscale Printing of Sensor Platforms for and Physiological Monitoring, Biomarker and Pathogen Detection Distinguished University Professor, W. L. Smith Professor and Director, NSF Nanoscale Science and Engineering center for


  1. Micro and Nanoscale Printing of Sensor Platforms for and Physiological Monitoring, Biomarker and Pathogen Detection Distinguished University Professor, W. L. Smith Professor and Director, NSF Nanoscale Science and Engineering center for High-rate Nanomanufacturing Northeastern University, Boston, MA, USA www.nanomanufacturing.us

  2. Motivation: Cost Financial and Environmental Cost Commercial electronics manufacturing is still expensive, with fabs costing up to 15 billions and requiring massive quantities of water and power. 1990s - $1B-$2B 2016 - $17B 2

  3. Motivation: Versatility Can we print any material on any substrate?

  4. Motivation: IoT (Industry 4.0) Opportunities IoT has five key verticals: Wearable Devices, Cars, Homes, Cities , and the Industrial Internet. Impact by 2025 is $3.9-$11.1 Trillions. The IoT can only be enabled by • Industrial Internet breakthroughs in the cost of ubiquitous sensors for collecting and • Connected Cities sharing data • Connected Homes • Connected Cars • Wearables The four industrial revolutions & Industry 4.0; Industrial Internet The Goldman Sachs Group, Inc. Global Investment Research (2014)

  5. What is the State of the Art of the Current Printing Technologies?  Current electronics and 3D printing using inkjet technology is only used to print antennas for electronics and they can only print down to 20 microns (20,000 nanometers).  20 microns was the silicon electronics scale (line width) in 1975.  Cost of a currently printed electronics is 10 to 100 times less than the cost of current silicon-based sensors.  A printing technology is needed that can print conductive, semiconducting, and insulating materials (inorganic or organic) down to 20nm and 1000 times faster than inkjet.  There is need to print Inter- connected multilayers.

  6. Beyond 3-D & Electronic Printing: Nanoscale Offset Printing Advantages  Additive  High throughput  Prints down to 20nm  Room temperature and pressure  Prints on flexible or hard substrates  Multi-scale; nano to macro  Material independent  Very low energy consumption  Very low capital investment Advanced Materials, 2015, 27, pp. 1759 – 1766.

  7. Damascene Templates for Nanoscale Offset Printing SiO 2 W PEN PI Polymer-based Silicon- Templates based Hard Templates Advanced Materials, 2015 Assembled Particles Assembled SWNT

  8. Directed Assembly-based Printing of Interconnects ACS Nano, April 2014 • Manufacturing of 3-D nanostructures using directed nanoparticle assembly process. (A and B) NPs suspended in aqueous solution are ( A) assembled and ( B) fused in the patterned via geometries under an applied AC electric field. ( C) Removal of the patterned insulator film after the assembly process produces arrays of 3-D nanostructures on the surface. (D) Scanning electron microscopy (SEM) image of gold nanopillar arrays . 使用纳米颗粒定向自组装工艺制造 3D 纳米结构。( A 和 B )水溶液中的纳米颗粒在交流电场的作用下被组装( A )到孔形的结构中,并熔化( B )形成纳米柱。( C )组装结束后,去除用于形成孔形结构的绝缘薄膜就会出现成列的 3D 纳米结构。( D )金纳米柱阵列的扫描电镜图片。 • MC Roco, Nov 2 2014

  9. Assembly of NPs into Trench and Vias Over Large Areas Particle: 30nm fluorescent (green) silica NPs Assembly time: <10 min 10 µm No electrophoretic or Di electrophoretic force is used.

  10. Demonstrated Printed Applications What� Could� We� manufacture� with� Mul scale� Offset� Prin ng?� CNTs for SWNT & NP Energy Interconnects Harvesting Flexible Assembly of SWNT NEMS & Electronics CNTs and NPs MoS2 devices for Batteries Multi- 2-D Assembly of biomarker Structural Apps. Biosensors Energy Electronics Antennas, EMI Materials Bio/Med Shielding, Drug Radar, Delivery Metamaterials Directed Assembly and Transfer 1 0 Nanoscale Science � � m m

  11. Fully Automated Nanoscale Offset Printing System (NanoOPS) Prototype was Demonstrated to more than 70 companies  The World’s First Nano Printer with integrated registration and alignment. NanoOPS Videos on Youtube: NanoOPS� Includes� Six� 5 2 Modules:� From Lab to Fab: Pioneers in Nano- � 1 1.� Hexagon� Frame� Module� Manufacturing � 2.� Template� Load� Port� Module� 6 https://www.youtube.com/watch?v=tZeO9I1KEec � 3.� Directed� Assembly� Module� � 4.� Mask� Aligner� Module� NanoOPS at Northeastern University � 5.� Transfer� Module� https://www.youtube.com/watch?v=2iEjIcog774 � 6.� Template� Load� Port� Module� NanoOPS - A Nanomanufacturing Breakthrough 3 4 https://www.youtube.com/watch?v=J4XupF3Zt5U

  12. The World’s First Nanoscale Printer for Electronics Awards and Publicity Printed Electronics Conf., Berlin 2016 The world’s first Nanoscale Printing System for electronics and sensors. NanoOPS� Includes� Six� 5 2 Modules:� � 1 1.� Hexagon� Frame� Module� � 2.� Template� Load� Port� Module� 6 � 3.� Directed� Assembly� Module� � 4.� Mask� Aligner� Module� � 5.� Transfer� Module� � 6.� Template� Load� Port� Module� 3 4 1000 times faster printing with a 1000 times smaller features than inkjet or 3D printing. NanoOPS Videos on Youtube: From Lab to Fab: Pioneers in Nano-Manufacturing : https://www.youtube.com/watch?v=tZeO9I1KEec 12 NanoOPS at Northeastern University : https://www.youtube.com/watch?v=2iEjIcog774

  13. Sensors and Electronics at a Fraction of their Current Cost Sensors for Chemicals Sensors for E. coli bacteria, viruses, and other pathogens Functionalized SWNTs Cancer and cardiac 4 diseases. 25 μ 0 Detection limit μ m m is 200 times lower than Current Band-Aid sensor technology Supporting printed electronics for sensor systems

  14. Applications Electronics

  15. Electronics  Flexible transparent n-type MoS 2 transistors  Heterogeneous SWNTs and MoS 2 complimentary invertors SWNTs 1 μ m MoS 2 100 nm Nanotechnology , Vol. 23, (2012).  Rose Bengal Molecular Doping of CNT Transistors Appl. Phys. Lett. 97, 1 2010. Nanotechnology, Vol. 22, (2011)

  16. Sensors

  17. Chemical Sensors SEM images setup for assembled SWCNT array devices. (e) An optical image of wafer scale sensor devices. (f) Chemical structure of TEMPO molecules. (g) Real-time current changes as a function of conc. H 2 S gas at 10, 25, 50, 75 and 100 ppm for the functionalized SWCNT sensor. Analyst , 138, December 2013, Issue 23, pp.7206-7211

  18. How does state of the art compares? The Sensors developed by the CHN Commercial Sensors Weight: 0.000220462 lbs Weight: 5.5 lbs Weight: 4.15 lbs ($0.5) Commercial Chemical Hydrogen Our Chemical Hydrogen Sulfide (H2S) Sensors Sulfide (H2S) Sensors ($400-$500) Functionali zed SWNTs 4 25 0 μ μ m m Commercial Glucose Our “Band - Aid” sensor uses sweat or tears to detect glucose. Sensors use blood And can be used to detect viruses, bacteria, cancer, etc.  Current Sensors are large and consume more energy  Most sensors are not wearable, flexible or wireless

  19. Benefits of continuous glucose sensing ECONOMIC BURDEN Biomarker Associated disorder 300 245 High muscle lactate levels Muscle fatigue, ischemia 250 200 Billion $ High blood glucose levels Diabetes 125 150 100  Diabetes requires strict monitoring 46 50 9 0 of blood glucose levels. Coronoary Muscle Diabetes Cancer Disease Fatigue  Non-invasive, continuous monitoring can provide keen measurement and therapy.  Sweat provides a good pathway for non-invasive sensing.  Sensors can also be used to aid Source: FAQ How adopt a healthier lifestyle. Chao Chen, RSC Adv., 2013,3, 4473-4491

  20. Lactate Sensor Design Enzymatic Printed Aligned functionalization MWCNTs Polymer

  21. Monitoring Glucose, Lactate and Urea in Sweat 1 st day 0.12 0.20 2 nd day 0.20 3 rd day 1st day 1st day 0.16 7 th day 0.09 3rd day 0.15 2nd day 8 th day Current (  A) 6th day Current (  A) Current (  A) 3rd day 0.12 9 th day 0.06 6th day 0.10 8th day 11 th day 0.08 8th day 10th day 13 th day 9th day 0.03 16 th day 0.05 12th day 0.04 13th day 18 th day 14th day 14th day 0.00 20 th day 0.00 0.00 0.0 1.0 2.0 3.0 4.0 5.0 0 4 8 12 16 20 0 10 20 30 40 50 22 th day Lactate (g/L) D-glucose (mM) Urea (mg/dL) D-glucose L-lactate Urea Redesigned glucose sensor for detection in sweat

  22. Lactate Sensor Calibration and Testing * Sensor was used over a week before these results were obtained.

  23. Lactate Testing in 1X PBS: Baseline stability decreases over a week Batch 1 1 (Se (Sensor A) ) – Day 1 52 10 mM 5 mM (uA) 2 mM Current (uA) 51 50 Curr 49 0 100 200 300 400 Time (s Tim (s) Stable Batch 1 (Sensor A) – Day 7 Batch 1 (Sensor A) – Day 10 10 mM 10 mM 49.5 53.5 2 mM 5 mM 5 mM 20 mM 2 mM Current (uA) Current (uA) 49 53 48.5 52.5 48 52 47.5 47 51.5 0 200 400 600 0 200 400 600 800 Time (s) Time (s) Drift

  24. Lactate Sensor Specificity (1X PBS) Specificity Test – Day 1 52.4 52.2 52 Glucose 60uM 51.8 Current (uA) 51.6 9 mM Lactate Uric acid 51.4 51.2 51 50.8 50.6 50.4 0 50 100 150 200 250 300 350 400 Time (s)

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