LECTURE 15-4

Metal and Metal Oxide Nanowires

Maj Md. Ashrafuzzaman, Ph.D

1
Design of Zinc Oxide Tetrapod Devices
 ZnO & ZrO
• The unique characteristics of ZnO nanomaterials
(wide band gap, piezoelectric effect) lends them
great potential for UV and pressure sensing
applications.
• Nanomaterials require precise structural and
electrical characterization which are complicated
by their size.
• In order to use ZnO nanostructures successfully
in macro-scale devices, we must develop
effective means to integrate nanostructures into
a working device.
 Nanoparticle Applications: ZrO
• Zirconium Dioxide nanoparticles can
increase the tensile strength of materials
when applied as a coating.
• This has many possible applications in
wear coatings, ceramics, dies, cutting
edges, as well as piezoelectric
components, and dielectrics.
 Synthesis of the Nanostructures
Used Vapor Phase Transport Method

Furnace
Valves
O2 Ar

• Argon and Oxygen gas flow

• Bubbles per minute controlled the rate
Glass Tube • Inside the tube, solid reagents were
placed in the boat.
Gas Flow • In some runs, Si wafers with gold
catalyst were placed downstream from
the boat.
Alumina Boat
 Processing Condition A: No Wafer
• Solid Reagents: Zn metal powder
• Gas Flow: Ar- 30 bubbles/min O2- 10
bubbles/min
• 850 Celsius and held for 90 minutes.
• Initially only Ar gas, then turn on O2 gas when
system reached 410 degrees.
• Results show a fluffy white product throughout
much of the tube.
• See Zinc Oxide Tetrapod Structures (ZOT) from
ESEM images:

Scale Bar: 20μm Scale Bar: 5μm

 Processing Condition B: Colloidal Gold
•Reasoning: Instead of Zn and O2 reacting Si Wafer, Scale Bar: 1μm

in air (or on the glass tube/ceramic boat) to

form tetrapods, a catalyst-induced
nucleation may cause linear rods to grow.

•Cytimmune: 26 nm in 133 μg/ml H20

•Applied colloid to Si and GaN wafers.

•Placed Zn powder in boat and wafers

GaN Wafer, Scale Bar: 1μm
downstream from boat. Same gas flow and
temperature conditions as Experiment A
 Processing Condition C:
ZnO and Graphite with Colloidal Gold
• ZnO and graphite source material
instead of Zn powder.
• Use 1:1 ratio of ZnO and graphite Scale Bar: 2 μm
powder. Only use Argon for gas flow.
Heat to 900 degrees and dwell for 90
minutes.
• Mechanism: ZnO powder is reduced by
graphite to form Zn and CO vapor at
high T (carbothermal reduction).

• Zn vapor flows downstream to form

alloy with Au colloid.
• Vapor-Liquid-Solid growth: ZnO
nanowires form, possibly from Zn and
CO reaction.

Tube setup from left: GaN, Si, Boat with mixed 1:1 ratio of ZnO and graphite
 Processing Condition D: Gold Coated Wafers
• Motivation: a uniform 10 nm gold-
coated Si wafer will induce better
nucleation sites for nanorod growth
than colloidal gold
• Used ZnO and C powder with Ar and
O2 gas
• Heated to 900 Celsius
• See rod-like structures, forming more
material than with gold colloid
processing conditions.

Scale Bar: 10μm

Conclusions from nanostructure synthesis:
•Processing Condition A (without wafer)
produced high yield of ZnO tetrapods
(ZOTs).
•Methods employing wafers with gold colloid
or coating were able to grow nanorods, but
not in high enough yield to collect and use
in devices.
•All devices used ZOTs fabricated from
processing condition A.
 Horizontal and Vertical Device Concepts
Horizontal Device Top View Vertical Device Cross Section

Figure A

Figure B

• In both figures, the light blue area

• In Figure A, the unaligned indicates nanomaterial, yellow block
nanostructures are placed show the polymer matrix, and dark blue
between two electrodes. shapes represent the electrodes

• In Figure B, a pattern is used to • One concept involved use of a patterned

catalyst (red) to grow vertically aligned
induce alignment in rod-like nanorods.
nanomaterial.
 Horizontal Device Processing Photoresist
Active Area

Trenches

Contact Holes Au Electrode

• Multiple electrode variations were fabricated

• Common features include a protective layer of photoresist to cover the electrodes and two holes in
the layer to provide contact points
• One version had trenches between the electrodes. If a polymer-dispersed method was used, the
trenches were intended to keep the liquid dispersed nanomaterial in place.
• Another version has one open field between the electrodes.
• Two masks were used to create each electrode design
 Integrating Nanomaterial into
Device
• Langmuir-Blodgett and integration via PDMS fluidic flows
were investigated. These techniques were considered
too complex for our time frame.
• Polymer matrix dispersions chosen
• Various polymers were researched and utilized in
experiments
Kapton PDMS PVA Glue

Jung, et al. Nano Letters,

www2.dupont.com/Kapton/en_US/assets/downloads/pdf/su Vol.,6, No. 3 413-418.
mmaryofprop.pdf
 First Device Design
Scale Bar: 20μm
• Two silver paint contacts on
a microscope slide ~½ inch
apart.
• A pile of ZOT was placed in
between (see A).
• More silver paint was
applied at the contact
regions (see B).

An ESEM image of the Ag contact / ZOT interface .

Scale Bar: 5μm

B
A higher magnification of the Ag / ZOT interface. The arrow
indicates a ZOT arm clearly embedded in the contact metal..
 Proof of Concept: Initial Device Testing

• The device was tested on

the probe station in the
Kim Building teaching lab.
• Force was applied by
hand with a glass rod
laying across the
nanoparticles.
• Light was applied with a
lamp at the work station
• From both tests we saw
electrical response and
decided to investigate
pressure applications of
ZnO nanostructures
 Considerations: Pressure Device
• Before we integrated the ZOT into our microdevice we needed to
test several approaches by making macrodevices using:
– Kapton Tape
– PDMS
– Poly Vinyl Acetate Glue
• The qualitative results obtained from these macrodevices would
allow us to select the best method of integration into our
microdevices.
• Considerations we wanted to address in our macrodevice were:
– ZOT connectivity in the given integration method
– Noticeable electrical response to stimuli
– Structural Stability of the device
– Ease of integration into microdevice
 Zinc Oxide Tetrapods (ZOT) in PDMS
• For our pressure sensing device,
we investigated two devices that
used PDMS. The first device
contained a mixture of PDMS
and the ZOT powder

The IV curve of 29 wt. % ZOT shows a lack of

repeatability. It was determined through ESEM
images that there was little connectivity between
the dispersed ZOT at this wt.% High wt.% designs
were too mechanically unstable to test.

29 wt. % ZOT suspended in PDMS

 PDMS Cover Design
• Pile of ZOT (similar to device
one) covered with PDMS and
degassed.
• When we reversed the device,
unique characteristics were
observed as shown in the
curve
ZOT powder covered with PDMS
• From this device we concluded
that: IV C urve P DMS C over on ZOT

– When we reversed the

6.00E -09

5.00E -09

polarities, the results were not 4.00E -09

reproducible
3.00E -09

C urrent (Am ps )
2.00E -09

1.00E -09 0

– There was a noticeable -15 -10 -5

0.00E + 00
0 5 10 15

response to pressure -1.00E -09

-2.00E -09

– These unique characteristics -3.00E -09

V olta g e (v)

were too complex for our

Tes t 1 Tes t 2 (R evers al)
Tes t 3 (s ec ond revers al tes t) Tes t 4 (40.996 grams )

timeframe
 Kapton Tape over Nanorods
• For our second device we decided to essentially bundle the
nanostructures with Kapton tape
• From our tests we concluded that there is an electrical
response with the application of pressure within the device
but integration of the Kapton tape into a microdevice would
be very difficult

IV Curves for Kapton Tape

8.00E-10

6.00E-10

4.00E-10
Current (Amps)

2.00E-10
Applied Force Test 1
0.00E+00 Applied Force Test 2
-6 -4 -2 0 2 4 6 No Force Applied
-2.00E-10

-4.00E-10

-6.00E-10

-8.00E-10
Voltage (V)
 PVA Adhesive and ZOT
IV Curves for Glue Pressure Tests
• Neutral pH adhesive (polyvinyl
acetate based; PVA) was 3.00E-07

diluted with water 2.50E-07

2.00E-07
• Integration Methods: 1.50E-07

– dripping diluted glue onto 1.00E-07

Current (Amps)
No Pressure
5.00E-08 First Pressure Test
the powder in place 0.00E+00 Second Pressure Test

– mixing a slurry of glue, -6 -4 -2

-5.00E-08
0 2 4 6

water and ZOT and -1.00E-07

depositing this on the -1.50E-07

-2.00E-07
substrate. Voltage (V)

• From this we concluded:

– The nanorods had an
electrical response with the
application of pressure
– There was relative ease in
making the device
– That we had created a
structurally stable structure
 Device Selection
• From the qualitative data obtained from
the macrodevices, decided to further
development of a microdevice using PVA
glue as an integration staple because:
– It would be easiest to integrate
– There was discernable electrical response
(which allowed to assume there was good
conductivity)
– The structure of the device was stable
Quantifying Pressure Sensing
• In order to adequately access whether the conductance/resistance
is changing with pressure we made a special platform that allowed
us to apply quantifiable pressure on top of a device.
• What we expect is that the conductance should decrease with the
application of pressure

Apparatus created to apply quantifiable

pressure on device. Rubber tip diameter is
3mm
 Pressure Testing: Glue Dispersed Powder
on the Au Patterned Electrodes
Pressure on Glue-Dispersed ZnO - Trial 1

3.00E-05

2.00E-05
Increasing Pressure

1.00E-05
1kPa
3kPa
Amps

0.00E+00 4.5kPa
6kPa
-4.5 -3.5 -2.5 -1.5 -0.5 0.5 1.5 2.5 3.5 4.5
9kPa
-1.00E-05 15kPa

-2.00E-05
Increasing Pressure

-3.00E-05
Volts

As the applied pressure increases, a noticeable decrease in the slope is

 Pressure Testing: Glue Dispersed Powder
on the Au Patterned Electrodes

Pressure on Glue-Dispersed ZnO

2.40E+05

2.20E+05

2.00E+05 1kN
Resistance (ohms)

Increasing Pressure 3kN

1.80E+05
Increasing Resistance 4.5kN
6kN
1.60E+05
9kN
1.40E+05 15kN

1.20E+05

1.00E+05
-4.5 -3.5 -2.5 -1.5 -0.5 0.5 1.5 2.5 3.5 4.5
Volts

Resistance varies with pressure between 1.5 and 3.5 V in both positive and negative
regions.
 Future Work
• Better apparatus for applying quantifiable
pressure
• Worth quantitatively investigating capacitance as
a function of voltage
• Comparing electrical and piezoelectric response
of nanorods versus tetrapods
• Modeling pressure versus resistance from data
we obtain is necessary in order to:
– Make a predictable device
– Understand the nanomechanics of ZOT PVA
composite
 Summary
• Synthesized nanorods and tetrapods using vapor
transport growth
• Used lithography to create two horizontal electrode
designs on silicon wafers
• Integrated tetrapods into macroscale devices with:
– Kapton Tape
– PDMS
– PVA Glue
• Observed I-V response to pressure and light stimuli in
devices
• Quantified pressure effects on resistance on a wafer
device