Using Piezoelectric Printing to Pattern Nanoparticle ThinfilmsUsing Piezoelectric Printing to Pattern Nanoparticle Thinfilms Jan Sumerel, Ph.D. FUJIFILM Dimatix, Inc. Santa Clara,

Using Piezoelectric Printing to Pattern Nanoparticle Thinfilms

Jan Sumerel, Ph.D.FUJIFILM Dimatix, Inc.Santa Clara, California

USA

Acknowledgements

• Vanderbilt University– David Wright– Leila Deravi– Sarah Sewell– Aren Gerdon

• University of North Carolina, Chapel Hill– Roger Narayan– Andy Doraiswamy

• NASA Ames– Cattien Nguyen

• Santa Clara University– Angel Islas– John Choy

Nanoscale Engineering"Nanotechnology is the understanding and control of matter at dimensions of roughly 1 to 100 nanometers, where unique phenomena enable novel applications."

(U.S. National Nanotechnology Initiative: www.nano.gov)

Therefore nanoscale engineering is the design, analysis, and/or construction of materials containing nanostructures.

Dimatix Materials Printer

Simple Biosensor

A hybrid device with both inorganic and organic materials

Using Ink Jet Printing as Straightforward Technique for Nanomaterial Thinfilm Production

Drop on DemandmwCNTs

Contact angle determines wettability(drop spread) of mwCNTs

13.10

Contact Angle (º)

Bioinks

•Bacterial Cells•Yeast•Proteins•Nucleic Acids•DNA scaffolds

Piezoelectric Ink Jetting Biological MaterialsAre there obstacles?

• Often aqueous solutions– High surface tension – Water = 72.8 dynes/cm

• Low viscosity – 0.89 – 3.00 centipoise

• “Friendly”surfactants?– CMC

http://serve.me.nus.edu.sg/siggi/marangoni_instability_of_a_water.htm

Water on glycerin

BioinksAre they non-Newtonian fluids?

www.wikipedia.com

What happens to a Fluid in the Shear Field Environment?

Relative sizes of Matter and Order of Magnitude

http://micro.magnet.fsu.edu/cells/index.html

Piezoelectric Inkjet Printing of 3.2 kBplasmid DNA

Repeatability of Ink Jetted Genomic DNA and PCR amplification

Streptavidin Printed in Methyl Cellulose Gel Retains Tertiary Structure

Fourier Transform Infrared Spectroscopy

Cy3 IgG Protein Array

No

DH10B Bacterial Cells

Other Sensor Components

• Quantum Dots• Electroinks

– Conductive Silver Precursor Fluids– PEDOT/PSS– Carbon Nanotubes

Ink Jet Printing Quantum Dots Inks

• Quantum Dots from UT Dots

• TEM from UT Dots• 2.6 nm green

emission• 4.0 nm

yellow/orange emission

Contact Angles of Quantum Dot Inks

2.6 nm 6 mg/mL 4.0 nm 3 mg/mL

Fluid Characteristics After Printing 2.6 nm 6 mg/mL

4.0 nm 3 mg/mL

Quantum Dot Inks on Substrate

Contributions to 3D structure dependent on particle concentration and particle size

Ink Jets Print Conductive Patterns for RFID, Electronics, PCBs, and Displays

• Conductive Silver Precursors• PEDOT/PSS• Carbon Nanotubes

Nanoparticle Polydispersity of ANP Conductive Silver Precursor Fluid as Shown by TEM

254 μm Grid Spacing Matrix55% Silver Conductive Ink

10 pL 1 pL

Waveform Employed for ANP Conductive Silver Fluid Precursor

A. B.

Resulting Conductive Silver Thinfilms on Teslin

Before Annealing After Annealing

Atomic Force Microscopy Shows Silver Nanoparticle Film Feature Sizes on Silicon Wafer

Feature width = 40.6 μmFeature height = 1.6 μ m

Feature Sizes Obtained with ANP Conductive Silver Precursor on Kapton®

Surface Measurements of 1 pL drop

Before annealing

After annealing

A. B.

Resistance Measurements for Commercially Available Conductive Silver Precursors

Cabot Conductive Silver Precursor InkANP Conductive Silver Precursor Ink

Gold Nanoparticle InkApplications in Nanobioengineering

Gold binds to proteins via two different mechanisms

•Cysteine residue•Serine, Threonine residues

Braun, Sarikaya and Schulten, Univ. IL

PEDOT/PSS Array on Glass Wafer

Other Sensor Components

PEDOT/PSS as the Fluid Leaves the Nozzles and Time of Flight

In flight(9.26 m/s)

A. B. C.

Contact Angles of PEDOT/PSS and ANP Silver Ink

A. B. C.Glass Wafer Kapton® Polyimide Teslin synthetic film

Electric Luminescence of Polyflourene printed on Silicon Wafer

Bright Field Dark Field + UV

Using Ink Jet Printing as Straightforward Technique for Nanomaterial Thinfilm Production

Drop on DemandmwCNTs

Contact angle determines wettability(drop spread) of mwCNTs

13.10

Contact Angle (º)

Multiwall Carbon Nanotube Scaffold for DNA

Bright Field DAPI

A B

Self-Assembling Biomaterials• Length scale

– Atoms (10-10)– Molecules (10-10-10-9) – Polymers (10-9)– Viruses (10-8)– Cells (10-5)– Multicellular organisms (10-5-101)

• Polymers– DNA – RNA– Proteins– Lipid bilayers self-assemble into membranes– Higher level organization (protein insertion into

membrane)– Trafficking– Extracellular matrices– Support structures (skeleton, teeth, antlers, husks)

• SECRETIONwww.azonano.com

Harnessing Nature’s Methods to Produce 3D Inorganic Materials

• Diatoms• Glass Sponges• Teeth• Bones

Silaffin of the Cylindrotheca fusiformis diatom

Using Ink Jet Printing for Thinfilm PatterningSilica Precipitating Amine Templates

N N

HN O

HN O

NHO

NHO

N

N

N

N

HN

HN

HN

HN

NH

NH

NH

NH

O

O

O O

O

O

OO

H2N

NH2

H2N

NH2

NH2

NH2

NH2

H2N

Polyamidoamino (PAMAM) Dendrimer

Kroger, N., et al. Science, 1999, 286, 1129.Knecht, M. R., Wright, D. W. Langmuir. 2004, 20, 4728.

H3N S S K K S G S Y

HO3PO OPO3H OPO3H

NH2

NH2

N

NH

NH

n = 4 - 9

S G S K G S K COO

33% G4 PAMAM Dendrimer

39.25785.333.1

Horizontal length (µm)

Vert height (nm)

Contact Angle (º)

100 µm

Stroboscopic View of the Dendrimer Ink Droplets.

Patterned Dendrimers

360 µm

360 µm

96 µm spacing, printed 4x with 35 seconds of lag time in between each printing cycle followed by 2 printing cycles s p a c e d a t 6 4 µ m .

1. 64 µm spacing, printed 2x with no lag time. 2. 56 µm spacing, printed 2x with no lag time.

1.

2.

Dendrimer ReactivityDendrimer Reactivity

• Once printed, we propose a “single spot”reaction vessel, wherein printed NH2 -terminated dendrimers will reproducibly yield concentrated areas of SiO2 nanospheres.

++

+ ++

+ +

+ +

+++

++-Si(OH)-Si(OH)

-Si(OH)

-Si(OH)

-Si(OH)

-Si(OH)-Si(OH)

-Si(OH)

Patterned Silica 160 nm Thinfilm Using Ink Jetted Dendrimers as Biomimetic Catalyst

15 20 25 30 35 400

200

400

600

800

1000

1200

1400

1600

nmol

es o

f sili

ca p

rodu

ced

total area of printed material (mm2)

Post-Si condensation

Pre-Si condensation

Conclusions• Nanoparticle Inks

– Conductive Silver Precursor Fluids

– PEDOT/PSS – Carbon Nanotubes

• Bioinks– Proteins – Nucleic Acids– Scaffolding materials

• Templating Organic Materials– Inorganic/organic thinfilms

• Modern Building Materials based on Biomimetics– Surfaces– Structures