Dip-Pen Nanolithography®: from the Lab to the Factory Floor Nanomanufacturing Summit 2009 May 29, 2009

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Dip-Pen Nanolithography®: From the Lab to the Factory Floor Nanomanufacturing Summit 2009 May 29, 2009

Copyright © 2009 NanoInk, Inc. Outline • NanoInk Overview • Scanning Probe Lithography and the Development of Dip Pen Nanolithography • Key Considerations for Manufacturing • Evolution of DPN® Instrumentation, Methods and MEMS devices • Nanomanufacturing Examples • Conclusions

Copyright © 2009 NanoInk, Inc. Corporate Overview • NanoInk started operations in November 2001 with focus on commercializing Dip Pen Nanolithography Technology • First product, DPNWrite™, introduced June 2002 • 70 total employees • Two facilities: – Skokie Headquarters – California MEMS Manufacturing Facility • Patent portfolio of over 100 filings in 8 Countries (43 issued, 2 allowed)

Copyright © 2009 NanoInk, Inc. NanoInk Business Units NanoFabrication Systems • Provides Dip-Pen Nanolithography® instrumentation and process knowledge to our customers. Products include the DPN 5000 and NLP 2000 systems NanoGuardian • Product authentication using NanoEncryption™ technology to detect counterfeiting and illegal diversion of prescription drugs NanoStem Cell • Control of cell growth and differentiation utilizing DPN generated nanopatterns Nano BioDiscovery • High sensitivity and high throughput assay instruments and services for protein detection and discovery

Copyright © 2009 NanoInk, Inc. Fabrication Tools - Macro . Machine tools (material removal) . Mills . Lathes . Etc. . Molding and forming . Casting . Injection molding . Stamping . Plating . Welding . EDM . Laser machining

Copyright © 2009 NanoInk, Inc. Fabrication Tools - Nano . Photolithography . Scanning Beam Lithography . FIB . E-beam . Soft Lithography . Micro-contact printing . Nanoimprint Lithography . Scanning Probe Lithography . Oxidation lithography . Nanografting . Nanomachining . Dip Pen Nanolithography . Nanomanipulation - Zyvex

Copyright © 2009 NanoInk, Inc. The DPN Process Dip Pen Nanolithography is Ink-coated DPN pen NanoInk's patented process for deposition of nanoscale materials onto a substrate. The vehicle for Individual Ink deposition can include pyramidal molecule scanning probe microscope tips, hollow tips, and even tips on electronically actuated cantilevers. Water Meniscus Writing Direction Nanopatterned Ink

Substrate

High Resolution Versatile, Chemical and Material Flexibility

DPN

Easy to use: direct Efficient, scalable, write, ambient affordable, high- conditions throughput potential

Copyright © 2009 NanoInk, Inc. DPN Applications – Multiple Methods • Direct Write –Write the molecule of interest directly onto the surface as the ink • Templating –Write out an ink pattern in order to create, or attach, something else –Directed self-assembly • Resist Patterning –Use the ink as an etch resist Combines Top/Down and Bottom/Up Methods

• Rate – A limitation for Scanning Probe methods? – Need parallel operations for throughput – Automation • Quality – Input - component and material issues – Process – Output - metrology • Cost – Value proposition – Consider total cost of ownership

Copyright © 2009 NanoInk, Inc. Key Components of a DPN Nanomanufacturing System • Instrumentation – Hardware – Software • MEMS Devices – Pen systems – Inking systems • Chemistry – Ink – Substrate • Process

The NSCRIPTOR The DPN 5000 The NLP 2000

. 1st generation . 2nd generation instrument instrument . AFM-based . AFM-based . 3rd generation . Tripod piezo scanner . Flexure scanner instrument . No AFM; fixed pen mount . 40 mm range nanopositioning stage

> 300 µm range

. Parallel Probe arrays lead to higher throughput, large area patterning

1.3 million pens in a 4” wafer

90 µm

20 µm

Oxide- Sharpened DPN Probe, 15 nm tip radius F.O.T. = 19.5 µm

Top view schematic of the 2D nano PrintArray viewport configuration

5 mm

1 cm SEM top view image of the 2D nano PrintArray viewports.

Active Pens use thermal bimorph technology to individually approach and retract pens from the surface via computer control, integrated into the InkCAD software.

serpentine Active Pen Array heating element • 6 writing pens • 2 reader probes heat spreader . Cleanly address surface features . Print multi-ink patterns without cross- contamination . Use up to 6 different inks simultaneously . Avoid changing individual pens during experiments microwell

Inkwell chip 10 micron diameter With 2mm diameter microwell detail reservoirs

Copyright © 2009 NanoInk, Inc. Soft MEMS Tip (SMT) Arrays • Need exists for large area (5 mm2), homogeneous nanopatterned surfaces for cell growth and differentiation experiments (>300 million features) • Estimate that direct write with e-beam would require 5 hours and cost $6K • Current 55K pen arrays requires over 20,000 imprint operations and patterning time of 1 hour to cover area • A dramatic increase in parallel printing capability is required

Example 1: 500nm squares on 800 nm pitch

Top View

16 stamping events to give 200 nm pitch

Tip-to-tip spacing Number of Tips on Spot-to-spot Number of Spots on SMT die (nm) 7mm x 7mm die spacing on on 5mm x 5mm substrate (nm) substrate

800 76,562,500 200 625,000,000

1600 19,140,625 400 156,250,000

2000 12,250,000 800 100,000,000

• Hundreds of research publications describing DPN applications www.nanoink.net/d/Biblio_DPN_Applications_2008.pdf • Growing collection of technology and application notes from NanoInk www.nanoink.net/NanoFabLiterature.htm • DPN Forum www.dpnforum.com

• Photomask Repair • Protein Nanoarrays • Stem Cell Substrates

Conventional Microarray

200 um

DPN Microarray 2 mm

The feature size is 210nm ± 5 nm

The DPN process allows preparing tens of thousands of spots in an area occupied by one spot of a conventional array. The feature size and shape can be controlled by varying dwell time or writing speed.

Copyright © 2009 NanoInk, Inc. Nanoarray Benefits – Highly reproducible array features – Improved spot morphology – Less sample 6.6mm requirements – Low non-specific binding – Faster reaction kinetics – Standard protocols Alexa-Fluor488-HER2 Receptor Array

• 10 Different Cytokines Printed in Quadruplicate • Positive and Negative Controls in Quadruplicate • 16 Identical Sub- arrays

• Underlying issue in stem cell biology is the lack of defined, scalable, and controlled differentiation of stem cells into homogenous populations. • Protocols for stem cell differentiation are biochemical in nature and require extreme – hyper physiological – concentrations of growth factors and chemicals. • These biochemical protocols for generating differentiated stem cells are inefficient, resulting in low yields, unpredictable outcomes, and large cellular heterogeneity.

Cartilage Cells

Fat Cells

Brain DPN-Generated Nanopattern Cells

Copyright © 2009 NanoInk, Inc. Conclusions • Scanning Probe Tools are the CNC machining centers of nanofabrication • DPN is powerful and versatile example of the application of SPM in nanomanufacturing • MEMS is a key technology for managing the interface between the micro and nano scales • Rate, quality and cost requirements vary across different nanomanufacturing applications. • Evolution of DPN instrument systems, MEMS and methods has led to the use of DPN in a variety of nanomanufacturing applications. • Further improvements will continue to expand the applicability of DPN in nanomanufacturing.

Mike Nelson Sr. V.P., Engineering NanoInk, Inc. 8025 Searle Parkway Skokie, IL 60077 847-745-3602 [email protected]