Nanocoatings

-Ashwin Vijaysai

Vijaysai "Self-Cleaning Materials: Lotus Leaf-1

Inspired
Nanotechnology“, August 2008, Scientific
 Is this familiar???

http://www.eye-doctor.ca/Content/eyeglasses/lenses/nikon/seecoat/seecoat.aspx
Vijaysai 2
http://www.pbma-fl.com/rain-repellent.html
 Overview
• Significance of nano-coatings
• Why it is needed in MEMS
– Anti- stiction (lube)
– Improve lifetime
• Types of nano-coatings
• Various chemistries
– Compare to choose the ideal
– Observe aging of nano-coating
• Surface modification at TTU MEMS
lab
• Chloro-silane based SAM
– Hydrophobic coating- for MEMS
• {Alumina nanoparticle + Chloro-silane
based SAM}
– Superhydrophobic coating- for medical
fabric
Vijaysai 3
 Significance of nanocoating
urface Engineering

l d
ie

Better Nano-coatings
y
d
an
t y
i li
iab
l
, re
ime
-t
ife
l
s e
r ea
c
In performance
Vijaysai 4
 Stiction based failure
mechanisms
• In MEMS is large
• Stiction failure surface forces >
spring forces
• Common failure mechanisms due to
Adhesion energy
stiction are:
– Capillary forces
– Van der waals forces c = constant of force i
i
– Electrostatic forces depending on properties of
surface and environment
n= power of interaction
z = distance of separation
h(z)=Distribution of distance
between rough surfaces

* M. V. Spengen , “On the physics of stiction and its impact on the reliability of microstructures ”, J.
Adhesion Sci. Technol., Vol. 17, No. 4, pp. 563–582Vijaysai
, 2003 5
 Solutions for alleviating
stiction
• Design modification – dimple, curve,
FEM
• Roughening surface – selective etch,
skewness
• Anti-Stiction Coatings –
– Plasma deposited coatings
– Self-Assembled monolayers (SAM
Poly-Silicon MEMS
S.No. Coating Adhesion
coatings) type energy
1 OTS 30 µJ/m2
~–1000
Vaportimes
phase deposited
2 coatings
FDTS 8 µJ/m2
decrease
– Getters of 3 Untreated ~56 mJ/m2
energy! U. Srinivasan, M. R. Houston, R. T. Howe and R.
Maboudian, J. MEMS, 7, 252-260, 1998.
Significance of nanocoating
• In SUMMiT-V after final release step,
liquid in-between two poly-silicon
layers can cause failure.
» Solution: Critical point
drying________
» Future Problem: Capillary
condensation

• Anti-stiction coating (hydrophobic)

minimizes capillary condensation.
• Hydrophobic – fear of water
» eg: teflon cookware

Vijaysai 7
 Significance of nanocoating
High performance


HPCDdevices
•

Under actuation gap reduces ~. 05µ

TRA

Flexur Vijaysai 8
 Vapor Phase deposition of
For MEMS devices SAM
 under fabrication
the last few steps impact the yield,
reliability & functionality:
• Release step
– Critical point drying
– Avoid release stiction
• Surface preparation
– Surface cleaning (organic
contaminants)
– Asher/ Ashing/ UV-O cleaner
• Exposure
– Exposed to precursor
 (nano-coating chemistry)
Vijaysai 9
• Significance of nano-coatings
• Why it is needed in MEMS
– Anti- stiction (lube)
– Improve lifetime
In addition to:


• Dimples, roughness, straps, guides,

etc associated with design
• Process involved in SUMMiT-V
fabrication is not in our hands
• Surface chemistry involved in the
conformal treatment to all poly-
silicon layers helps
» Lower adhesion energy
» Increase reliability
Vijaysai  lifetime of device 10
 Common types of
nanocoatings
1.Chlorosilanes
2.Amines
3.Alcohols
4.Carboxylic acids
5.Siloxanes
6.Dimethylaminosilanes

* R. Ashurst et.al, “Vapor Phase Anti-stiction coating for MEMS”, Trans. on device and materials
reliability, vol.3, iss. 4, pp. 173-178, 2003.
Vijaysai 11
Vijaysai 12
 *

Hydrolysis reaction
1, some of the –OH groups participate in condensation
reaction with –OH group on the oxidized surface of the
silicon
2, Cross polymerization occurs between the individual
micelles
*Vapor-Phase Self-Assembled Monolayers for Anti-Stiction Applications in MEMS, Zhuanget al., J 13
MEMS,
Vijaysai
16, 6, 2007, pp. 1451-1460
Vijaysai 14
 Amines and Alcohols
• -Cl terminated Silicon surface is
obtatined by exposing –H
terminated Si sample to Cl2 in
vacuum  at 80℃ te m e ra tu re o f
sa m p le
• A m in e is –N H 2 eq ( 1 )
• A lco h o lis –O H e q ( 2 )

Vijaysai 15
 Siloxanes
 Analog devices – ADXL
accelerometers
1.During packaging step
2.Small aliquot dispensed inside
package
3.Package is sealed
4.Temperature of the chip is raised
Example : Demethyl siloxane
5.Liquid evaporates and forms organic
monolayer

Vijaysai 16
 Carboxylic acids
Texas Instruments – DMD chip


1.Perfluorinated –n- alkanoic acids (PFxA)

 ‘’ decnoic acid (PFDA)
• Minimize friction coefficient
• Minimize thermal decomposition
•
 Solid PFDA inside hermetic seal
 Sublimation of PFDA due to its vapor pressure
 Healing  one of its kind in MEMS package


 350 billion cycles

Vijaysai 17
 Dimethylaminosilanes
• PF8TAS S yn th e size d fro m :
• PF10TAS FO T S
FD T S

S im ila r p ro ce d u re a s in
ch lo ro sila n e s
B u t n o n e e d fo r w a te r va p o r/
w a te r in th e re a ctio n

Vijaysai 18
• Types of nano-coatings
• Various chemistries
– Compare to choose the ideal
– Observe aging of nano-coating

Vijaysai 19
At TTU – RPX 550, IST system

Vijaysai 20
Vijaysai 21
Vijaysai 22
Vijaysai 23
Vijaysai 24
Vijaysai 25
 Reaction Chemistry
• TMA (Alumina) Generation
3 3 + 3H20  Al203 + 6CH4
2Al(CH )

• Linkerrix generation (Linking chemistry,

that binds the TMA nano-particles)
SiCl
4 + 2H20  Si02+ 4HCl
C2H4Cl6Si2 + 6H20  SiOx-(CH2)2-SiOx +


6HCl +3H20
C6H12 Cl6Si2 + 6H20  SiOx-(CH2)2-SiOx +


6HCl +3H20
Vijaysai 26
Vijaysai 27
Nomenclature

Vijaysai 28
Comparison of contact
angle

Vijaysai 29
C o m p a riso n o f S ize

Vijaysai 30
 Magnified images of
superhydrophobic coating
SEM image of highly conformal coating

TEM image of alumina nano-particles.

Vijaysai 31
Vijaysai 32
RPX 550 System and initial
results * www.insurftech .com

FOTS

LDDMS VDDMS

* R. Ashurst et.al, “Vapor Phase Anti-stiction

coating for MEMS”, Trans. on device and
materials reliability, vol.3, iss. 4, pp. 173-178,
2003.
• Surface modification at TTU MEMS
lab
• Chloro-silane based SAM
– Hydrophobic coating- for MEMS
• {Alumina nanoparticle + Chloro-silane
based SAM}
– Superhydrophobic coating- for medical
fabric

Vijaysai 34
Vijaysai 35
 MEMS Tribogauge
Lateral
axis

riving comb
Normal
axis
Sense comb
Sense comb

AD7747 Measure
Eval LabView Displacement of ‘Head’, i.e,
Board fingers (as ‘C’)
 Baseline Stiction
TRIBOGAUGE MODEL
Model Approach
Maximum Retract
Displacement
Release
‘δ’ Displacement (µm)

Point
‘C’ Capacitance (fF)

,at contact of
119

slider and
3

scrubber
Maximum δ, C

0
D.C. Voltage (volts)
In - use
stiction
Adhesion  Static Friction , Static 37
 Nano-coating
characterization devices
/ techniques

Atomic Force Microscope:

1.Topography
2.Monolayer topography
3.Force – Distance measurement
4.Lateral force measurement

Vijaysai 38
Backup

Vijaysai 39
 Types of friction
ith respect to motion
Static friction is friction between two solid objects that are not moving relative to
each other. For example, static friction can prevent an object from sliding down a
sloped surface. The coefficient of static friction, typically denoted as μs, is usually
higher than the coefficient of kinetic friction.
The static friction force must be overcome by an applied force before an object can
move. The maximum possible friction force between two surfaces before sliding
begins is the product of the coefficient of static friction and the normal force: .

Kinetic (or dynamic) friction occurs when two objects are moving relative to each
other and rub together (like a sled on the ground). The coefficient of kinetic friction is
typically denoted as μk, and is usually less than the coefficient of static friction for
the same materials

wikipedia

Vijaysai 40
A1) Super-hydrophobicity is a combination of
roughness, coverage (aerial density) and surface
energy. So alumina nano-particles are very important
for roughness and how you distribute the nano-
particles over the surface. But you need to combine
this with low surface energy of the Phobix.

A2) The boulder formation that IST reports was

observed when using amine – epoxy adhesion versus a
linkerrix (oxide) adhesion. In the ATETATETA is
(A=amine step / T=TMA aluminum oxide / E=Epoxy) a
sequence. The durability was improved with Amine-T-
Epoxy reaction schemes. However, IST’s highest
durability was observed with a ALD layer.

Vijaysai 41