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 Demand
mwCNTs
Contact angle determines wettability
(drop spread) of mwCNTs
Contact
Angle (º)
13.10
Bioinks
•Bacterial Cells
•Yeast
•Proteins
•Nucleic Acids
•DNA scaffolds
Piezoelectric Ink Jetting Biological Materials
Are there obstacles?
• Often aqueous
solutions
– High surface tension
– Water = 72.8 dynes/cm
• Low viscosity
– 0.89 – 3.00 centipoise
• “Friendly”
surfactants?
– CMC
Water on glycerin
http://serve.me.nus.edu.sg/siggi/maran
goni_instability_of_a_water.htm
Bioinks
Are 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 kB
plasmid 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
N
o
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 Matrix
55% Silver Conductive Ink
10 pL
1 pL
Waveform Employed for ANP Conductive
Silver Fluid Precursor
Resulting Conductive Silver Thinfilms on Teslin
A.
B.
Before Annealing
After Annealing
Atomic Force Microscopy Shows Silver Nanoparticle
Film Feature Sizes on Silicon Wafer
Feature width = 40.6 μm
Feature 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
Resistance Measurements for Commercially
Available Conductive Silver Precursors
A.
B.
ANP Conductive Silver Precursor Ink
Cabot Conductive Silver Precursor Ink
Gold Nanoparticle Ink
Applications in Nanobioengineering
Gold binds to proteins via
two different mechanisms
•Cysteine residue
•Serine, Threonine
residues
Braun, Sarikaya and Schulten, Univ. IL
Other Sensor Components
PEDOT/PSS Array on Glass Wafer
PEDOT/PSS as the Fluid Leaves
the Nozzles and Time of Flight
In flight
(9.26 m/s)
Contact Angles of PEDOT/PSS and ANP Silver Ink
A.
B.
C.
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 Demand
mwCNTs
Contact angle determines wettability
(drop spread) of mwCNTs
Contact
Angle (º)
13.10
Multiwall Carbon Nanotube Scaffold for DNA
A
B
Bright Field
DAPI
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)
• SECRETION
www.azonano.com
Harnessing Nature’s Methods to
Produce 3D Inorganic Materials
•
•
•
•
Diatoms
Glass Sponges
Teeth
Bones
Using Ink Jet Printing for Thinfilm Patterning
Silica Precipitating Amine Templates
HO3PO
H3N
S
OPO3H
S
K
OPO3H
K
S
G
S
Y
S
G
S
K
G
S
K
COO
Silaffin of the Cylindrotheca fusiformis diatom
NH2
H 2N
NH
NH2
NH
O
HN
NH2
N
H
O
N
N
O
N
N
H 2N
NH
Polyamidoamino
(PAMAM)
Dendrimer
N
O
HN
H2N
O
NH
H
N
N
H
N
O
O
N
O
O
NH
NH2
HN
Kroger, N., et al. Science, 1999, 286, 1129.
Knecht, M. R., Wright, D. W. Langmuir. 2004, 20, 4728.
NH
O
HN
HN
n=4-9
O
NH2
O
NH2
NH2
33% G4 PAMAM Dendrimer
Contact
Angle (º)
Vert height
(nm)
Horizontal
length (µm)
33.1
785.3
39.25
Stroboscopic View of the
Dendrimer Ink Droplets.
100 µm
Patterned Dendrimers
1.
360 µm
2.
360 µm
1. 64 µm spacing, printed 2x with
no lag time. 2. 56 µm spacing,
printed 2x with no lag time.
96 µm spacing, printed 4x
with 35 seconds of lag time in
between each printing cycle
followed by 2 printing cycles
spaced at 64 µm.
Dendrimer 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
Pre-Si condensation
Post-Si condensation
1600
nmoles of silica produced
1400
1200
1000
800
600
400
200
0
15
20
25
30
35
2
total area of printed material (mm )
40
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