Synthesis and

Characterization of
nanomaterials

Prakash Chandra, PhD

Delhi Technological University
 How to get at nano scale?
There are two general approaches to the synthesis of
nanomaterials and the fabrication of nanostructures

Bottom-up approach Top-down approach

These approaches include the miniaturization These approaches use larger
of materials components (up to atomic level) (macroscopic) initial structures,
with further self assembly process leading to the which can be externally-
formation of nanostructures. controlled in the
During self-assembly the physical forces processing of nanostructures.
operating at nanoscale are used to combine basic Typical examples are etching
units into larger stable structures. through the mask, ball milling,
Typical examples are quantum dot formation and application of severe plastic
during epitaxial growth and formation of deformation.
nanoparticles from colloidal dispersion.
Top-down vs. bottom-up

Top-down methods
 begin with a pattern generated on a larger scale, then reduced to
nanoscale.
 By nature, aren’t cheap and quick to manufacture

- Slow and not suitable for large scale production.
 Bottom-up methods
 start with atoms or molecules and build up to nanostructures
 –Fabrication is much less expensive
Top-Down
 Motivation
MEMS
 MEMS = MicroElectroMechanical System
 Any engineering system that performs electrical and mechanical
functions with components in micrometers is a MEMS. (1 μm =
1/10 of human hair)
 MEMS products
 Microsensors- biomedical, chemical, inertia, optical, pressure, radiation,
thermal etc.
 Microactuator- Valve , Pumps, Microfluidics etc
 Read/Write heads in computer storage system
 Microdevices- Plamtop, Mini robots, microsurgical, Mobile telecome
etc.
 What is Lithography?
 Lithography is a process that uses focused radiant
energy and chemical films that are affected by this
energy to create precise temporary patterns in
silicon wafers or other materials.

 Lithography is an important part of the top-down

manufacturing process, since these temporary
patterns can be used to add or remove material
from a given area
 Types of Lithography
A. Photolithography (optical, UV, F. Step Growth
EUV) G. Soft Lithography
B. E-beam/ion-beam/Neutral H. Nanoimprint
atomic beam lithography
I. Shadow Mask
C. X-ray lithography
J. Self-Assembly
D. Interference lithography
K. Nanotemplates
E. Scanning Probe  Diblock copolymer
 Voltage pulse  Sphere
 CVD  Alumina membrane
 Local electrodeposition  Nanochannel glass
 Dip-pen  Nuclear-track etched
membrane
 Materials
 Fabrication of MEMS structures depends on
 structural, sacrificial, and masking materials on substrate,

 Issues related to etch selectivity, adhesion, microstructure, and

a host of other properties are important point of considerations

 Materials
silicon, glass, ceramics, polymers, compound
semiconductors, titanium and tungsten.
 Silicon
 Silicon (Si) is among the most abundant material on earth. It almost always
exists in compounds with other elements.
 Single crystal silicon is the most widely used substrate material for MEMS
and microsystems.
 The popularity of silicon for such application is primarily for the following
 reasons:
(1) It is mechanically stable and it is feasible to be integrated into electronics on
the same substrate (b/c it is a semiconducting material).
(2) Electronics for signal transduction such as the p or n-type piezoresistive can be
readily integrated with the Si substrate-ideal for transistors.
(3) Silicon is almost an ideal structure material. It has about the same Young’s
modulus as steel (∼ 2x105 MPa), but is as light as aluminum with a density
of about 2.3 g/cm3.
 Silicon
(4) It has a melting point at 1400oC, which is about twice higher than that of
aluminum. This high melting point makes silicon dimensionally stable even at
elevated temperature.
(5) Its thermal expansion coefficient is about 8 times smaller than that of steel,
and is more than 10 times smaller than that of aluminum.
(6) Silicon shows virtually no mechanical hysteresis. It is thus an ideal candidate
material for sensors and actuators.
(7) Silicon wafers are extremely flat for coatings and additional thin film layers
for either being integral structural parts, or performing precise
electromechanical functions.
(8) There is a greater flexibility in design and manufacture with silicon than
with other substrate materials. Treatments and fabrication processes for silicon
substrates are well established and documented.
 Single-Crystal Silicon
 For silicon to be used as a substrate material in integrated circuits and
MEMS, it has to be in a pure single-crystal form.
 The most commonly used method of producing single-crystal silicon
is the Czochralski (CZ) method.
The Czochralski method for producing single-
crystal silicon
(1) Raw Si (quartzite) + coal, coke, woodchips)
are melted in the crucible.
(2) A “seed” crystal is brought to be in contact
with molten Si to form larger crystal.
(3) The “puller” slowly pulls the molten Si up
to form pure Si “boule” after the solidification.
(4) The diameters of the “bologna-like” boules
vary from 100 mm (4”) to 300 mm (12”) in
diameters.
 Single-Crystal Silicon

Pure silicon wafers

Pure silicon boules of 300 mm

diameter and 30 ft long, can
weigh up to 400 Kg.
These boules are sliced into
thin disks (wafers) using
diamond saws.
Standard sizes of wafers are:
100 mm (4”) diameter x 500 μm thick.
150 mm (6”) diameter x 750 μm thick.
200 mm (8”) diameter x 1 mm thick
300 mm (12”) diameter x 750 μm thick (tentative).
 Single Silicon Crystal
Structure
Single silicon crystals are basically of “face-cubic-center” (FCC)
structure.
The crystal structure of a typical FCC crystal is shown below:

Total number of atoms: 8 at corners and 6 at faces = 14 atoms

 Single Silicon Crystal
Structure
 Single crystal silicon, however has 4 extra atoms in the interior.
 The situation is like to merge two FCC crystals together as shown below:

 Total no. of atoms in a single silicon crystal = 18.

 The unsymmetrical distribution of atoms within the crystal make pure
silicon anisotropic in its mechanical properties.
 In general, however, we treat silicon as an isotropic material.
3 Distinct Phases of cubic
crystal
 The 3 Principal Planes of a Silicon
Crystal

Characteristics of silicon by principal planes:

(1) The (100) planes contain least number of atoms→ the weakest plane → easiest to
work with.
(2) The (110) planes offers the cleanest surfaces in micro fabrications.
(3) The (111) contains shortest bonds between atoms → strongest plane→ toughest to
work with.
 Orientation and identification
flats

The primary flat is used for automated positioning of the wafer during subsequent
processing steps, e.g., lithographic patterning and dicing. Other smaller flats are called
"secondary flats" and are used to identify the crystal orientation , (<111> versus <100>)
and the material (n-type versus p-type)
(Bulk) Mechanical and
Thermophysical Properties of Silicon
Silicon Compounds
 There are 3 principal silicon compounds used in MEMS and
microsystems: Silicon dioxide (SiO2), Silicon carbide (SiC) and silicon
nitride (Si3N4) – each has distinct characteristic and unique applications.
Silicon dioxide (SiO2)
 It is least expensive material to offer good thermal and electrical
insulation.
 Also used a low-cost material for “masks” in micro fabrication processes
 such as etching, deposition and diffusion.
 Used as sacrificial material in “surface micromachining”.
 Above all, it is very easy to produce:
 - by dry heating of silicon: Si + O2 → SiO2
 - or by oxide silicon in wet steam: Si + 2H2O → SiO2 + 2H2
Silicon Compounds
 Silicon carbide (SiC)
 Its very high melting point and resistance to chemical reactions
make it ideal candidate material for being masks in micro fabrication
processes. It has superior dimensional stability.

 Silicon nitride (Si3N4)

 Used as excellent barrier to diffusion to water and ions.
 Its ultra strong resistance to oxidation and many etchants make it a
superior material for masks in deep etching.
 Also used as high strength electric insulators.
 Polycrystalline silicon

 It is usually called “Polysilicon”.

 It is an aggregation of pure silicon crystals with randomly
orientations deposited on the top of silicon substrates:

 These polysilicon usually are highly doped silicon.

 They are deposited to the substrate surfaces to produce localized “resistors”
and “gates for transistors”
 Being randomly oriented, polysilicon is even stronger than single silicon
crystals.
 Gallium Arsenide
(GaAs)
 GaAs is a compound simiconductor with equal number of Ga and As atoms.
 It is excellent material for monolithic integration of electronic and
photonic devices on a single substrate.
 The reason for being excellent material for photoelectronics is its high
electron mobility (7 times more mobile than silicon)
 GaAs is also a good thermal insulator.
 Low yield strength (only 1/3 of that of silicon) – “bad”.
 Quartz
 Quartz is a compound of SiO2.
 The single-unit cell is in shape of tetrahedron.
 Quartz is ideal material for sensors because of its extreme dimensional
stability.
 It is used as piezoelectric material in many devices.
 It is also excellent material for microfluics systems used in biomedical
applications.
 It offers excellent electric insulation in microsystems.
 A major disadvantage is its hard in machining. It is usually etched in
HF/NH4F into desired shapes.
 Quartz wafers up to 75 mm diameter by 100 μm thick are available
commercially.
 Piezoelectric Crystals
 Piezoelectric crystals are solid ceramic compounds that produce
piezoelectric effects:

 Natural piezoelectric crystals are: quartz, tourmaline and sodium

potassium tartrate.
 Synthesized crystals are: Rochelle salt, barium titanate and lead
 Polymers
 Polymers include: Plastics, adhesives, Plexiglass and Lucite.
 Principal applications of polymers in MEMS:
 Currently in biomedical applications and adhesive bonding.
 New applications involve using polymers as substrates with
electric conductivity made possible by doping.
 Molecular structure of polymers:
 It is made up of long chains of organic (hydrocarbon) molecules.
 The molecules can be as long as a few hundred nm.
 Characteristics of polymers:
 Low melting point; Poor electric conductivity
 Thermoplastics and thermosets are common industrial products
 Thermoplastics are easier to form into shapes.
 Thermosets have higher mechanical strength even at temperature up to 350 oC.
 Polymers as industrial
materials
 Polymers are popular materials used for many industrial products for
the following advantages:
 Light weight
 Ease in processing
 Low cost of raw materials and processes for producing polymers
 High corrosion resistance
 High electrical resistance
 High flexibility in structures
 High dimensional stability
Application of Polymers in
MEMS and microsysytem
(1) Photo-resist polymers are used to produce masks for creating desired
patterns on substrates by photolithography technique.
(2) The same photoresist polymers are used to produce the prime mold
with desirable geometry of the MEMS components in a LIGA process
(3) Conductive polymers are used as “organic” substrates for MEMS and
microsystems.
(4) The ferroelectric polymers that behave like piezoelectric crystals can
be used as the source of actuation in micro devices such as in micro
pumping.
(5) The thin Langmuir-Blodgett (LB) films can be used to produce
multilayer microstructures.
.
Application of Polymers in
MEMS and microsysytem
(6) Polymers with unique characteristics are used as coating substance to
capillary tubes to facilitate effective electro-osmotic flow in microfluidics
(7) Thin polymer films are used as electric insulators in micro devices,
and as dielectric substance in micro capacitors.
(8) They are widely used for electromagnetic interference (EMI) and radio
frequency interference (RFI) shielding in microsystems.
(9) Polymers are ideal materials for encapsulation of micro sensors and
the packaging of other microsystems.
 Conductive Polymers

Polymers are poor electric conducting materials by nature.

 Langmuir-Blodgett (LB)
films
 The process was first introduced by Langmuir in 1917 and Blodgett.
 The process involves the spreading volatile solvent over the surface-
active substrate materials.
 The LB process can produce more than one single monolayer by
depositing films of various compositions onto a substrate to produce a
multilayer structure.
 LB films are good candidate materials for exhibiting ferro (iron)- , pyro
(heat)- and piezoelectric properties. LB films may also be produced
with controlled optical properties such as refractive index and anti
reflections.
 They are thus ideal materials for micro sensors and optoelectronic
devices.
 eg. Poly-vinylidene fluoride (PVDF).
 MEMS PROCESS
 Same as the process steps used for making conventional
electronic circuits.
 Photolithography
 Photo means light, litho means (in greek) Stone and graphy
means Writing.

 Photolithography is used to produce images using light sensitive

photoresist and controlled exposure to light.

 Microlithography is the technique used to print ultra-miniature

patterns used primarily in the semiconductor industry.
Photo mask
CAD designs
 How are Masks made?
E-beam (electron-beam)
 Software Mask
direct writing

(UV)
Photoresist
 Photo sensitive material
 Temporarily coated on wafer surface
 Transfer design image on it through
exposure
 Very similar to the photo sensitive coating
on the film for camera
 Photoresist

Negative Photoresist Positive Photoresist

• Becomes insoluble after • Becomes soluble after
exposure exposure
• When developed, the • When developed, the
unexposed parts dissolved. exposed parts dissolved
• Cheaper • Better resolution
 Positive Photolithography
Areas exposed to light
become photosoluble.
Ultraviolet Light
Island
Chrome island
on glass mask Window
Shadow on
photoresist photoresist

Exposed area
of photoresist
oxide

photoresist silicon substrate

oxide

silicon substrate Resulting pattern after

the resist is developed.
Positive photoresist is used
 Negative Photolithography
Areas exposed to light
become polymerized and
Ultraviolet Light resist the develop chemical.
Chrome island
on glass mask Island
Exposed area
of photoresist
Window
photoresist
Shadow on
photoresist

photoresist
oxide oxide

silicon substrate silicon substrate

Resulting pattern after

the resist is developed.
Negative Photoresist is used
 Basic steps of
Photolithography

 Surface Preparation  Hard Bake

 Photoresist Application  Inspection
 Soft Bake  Etch
 Align the mask &  Resist Strip ( remove PR)
Expose PR to UV light*  Final Inspection
 Develop

* Some processes may include a Post-exposure Bake

 Surface Preparation
 Clean and dry wafer surface
(hydrophobic) HMDS
 Plasma oxidation (10
minutes) or Adhesion
promoters are used to assist
resist coating ex:
Hexamethyldisilazane
(HMDS)
 Temp ~ 200 - 250°C
 Time ~ 60 sec.
 Photoresist spin coating
 Wafer held onto vacuum chuck
 Dispense ~5ml of photoresist photoresist
dispenser
 Slow spin ~ 500 rpm
 Ramp up to ~ 3000 - 5000 rpm
 Quality measures:
 time
 speed
 thickness
 uniformity
 particles & defects vacuum chuck

to vacuum
pump spindle
 Softbake
 Partial evaporation of photo-
resist solvents
 Improves adhesion
 Improves uniformity
 Improves etch resistance
 Improves linewidth control
 Optimizes light absorbance
characteristics of photoresist
 Alignment & Exposure
 Alignment errors
(many different types)
 Mask aligner
equipment
 Double sided
alignment especially
important in
micromachines
Lithography systems-UV
light
 Alignment & Exposure
 Normally requires at least two alignment mark sets on
opposite sides of wafer or stepped region.

Use a split-field microscope to make alignment easier:
Mask Aligner Fixture
 Hard bake
 Evaporate remaining
photoresist

 Improve adhesion

 Higher temperature
than soft bake
 Developing the photoresist
 Soluble areas of photoresist are
dissolved by developer chemical developer
dispenser
 Visible patterns appear on
wafer

windows

islands
 Quality measures:

line resolution

uniformity
vacuum chuck

particles & defects
spindle
 Wafer inspection
 Optical or SEM metrology

 Quality issues:
 particles
 defects
 critical dimensions
 linewidth resolution
 overlay accuracy
Photolithography combined with
etching and thin film deposition
Plasma etch ( dry etching with plasma) -to remove the
photoresist
2 m x 2m x 2 m 2 m x 3m x 2 m 2 m x 15m x 2 m

2 m x 4m x 2 m 2 m x 5m x 2 m 2 m x 20m x 2 m

2 m x 7m x 2 m 2 m x 10m x 2 m
 Photolithography
Methods

Substrate spin coating Soft baking

Treatment SU-8 Photoresist

Plasma oxidation or Spin @ desired Speed

HMDS,

Exposure Post exposure Develop

to UV light Bake SU-8 Photoresist
Required time by supplier In chemical solvent

Hard bake SU-8

Rinse and dry Film removal

@150-200oC
Photolithography
Microfabrication Process
 Etching
 Bulk micromanufacturing technique involves creating 3-D
components
by removing materials from thick substrates (silicon or other
materials) using primarily etching method.
 Etching - dry or wet etching is the principal technique used in bulk
micromanufacturing.
 Substrates that can be etched in bulk micromanufacturing include:
Silicon , SiC, GaAs, special polymers
 Wet etching involves the use of chemical solvents (called etchants)
 Dry etching uses plasma to remove materials at the desired locations
on a substrate.
 Choosing a Method
 Choosing a method
 Desired shapes

 Etch depth and uniformity

 Surface roughness

 Process compatibility

 Safety, cost, availability,

environmental impact
 Isotropic and
Anisotropic etching
 When a material is attacked by a liquid or vapor etchant, it is removed
isotropically (uniformly in all directions) or anisotropic etching
(uniformity in vertical direction).

Anisotropy Isotropy
 Material removal rate for wet-etching is usually faster than the rates for
many dry etching processes
 Etching rate changed by varying temperature or the concentration of active
species.
 Isotropic and Anisotropic
etching
 Pure silicon crystals are not isotropic in their properties due to non-uniform
distribution of atoms at their interior.
 Such anisotropic properties are represented by three distinct planes.

 The (111) plane makes an angle of 54.74o with the (100) plane.
 Corresponding to these (3) planes are 3 distinct directions in which etching
takes place: <100>, <110> and <111>.
 The <100> is the easiest direction for etching, and the <111> is the hardest
direction for etching.
 Wet Etch
 Removal process that uses liquid chemicals or etchants to remove
materials from a wafer.
 The specific patters are defined by masks on the wafer.
 Materials that are not protected by the masks are etched away by
liquid chemicals.
 These masks are deposited and patterned on the wafers in a prior
fabrication step using lithography.
 Etching Chemistry
 A wet etching process involves multiple chemical reactions
 The wet etch process can be described by three basic steps.
(1) Diffusion of the liquid etchant to the structure that is to be removed.
(2) The reaction between the liquid etchant and the material being etched away. A
reduction-oxidation (redox) reaction usually occurs. This reaction entails
the oxidation of the material then dissolving the oxidized material.
(3) Diffusion of the byproducts in the reaction from the reacted surface
 Key ingredients in any wet etchant:
– Oxidizer
examples: H2O2, HNO3
– Acid or base to dissolve oxidized surface
examples: H2SO4, NH4OH
– Dillutent media to transport reactants and products through
examples: H2O, CH3COOH
Anisotropic wet etching
 Liquid etchants etch crystalline materials at different rates depending
upon which crystal face is exposed to the etchant .
 Depend on Si crystalline plane.
 Anisotropic etching is easier to control of the etched shape of the
substrates.
Anisotropic wet etching
 Alkaline chemicals with ph > 12 for anisotropic etching.
 Popular anisotropic etchants are:
 KOH ( potassium hydroxide)
 EDP (ethylene-diamine and pyrocatecol)
 TMAH (tetramethyl ammonium hydroxide)
 Hydrazine
 Most etchants are used with 1:1 by weight mixture with water.
 Typical etching rates are:
Hydroxide Etching of
Silicon
 Isotropy Wet etching
 For isotropic wet etching, a mixture of hydrofluoric acid, nitric acid,
and acetic acid (HNA) is the most common etchant solvent for silicon.
 The concentrations of each etchant determines the etch rate.
 Silicon dioxide or silicon nitride is usually used as a masking material
against HNA.
 Silicon compounds are much stronger etching resistive materials than
silicon.
 These materials can thus be used as masks for etching of silicon
substrates.
“Wet chemical etching is generally isotropic even though a mask is
present since the liquid etchant can penetrate underneath the mask. If
directionality is very important for high-resolution pattern transfer,
wet chemical etching is normally not used. “
 Etch stop
 Etch Stop refers to stopping the etching reaction be it isotropic or
anisotropic at a desired point.
There are two categories for etch stop –
1. Time based etch stop
Etching is stopped by removing the wafer from the etching solution at a certain time.
2. Selectivity based etch stop

Etching may be stopped by the following two methods, both related to
doping of the silicon substrates.
 Controlled by doping:

Doped silicon dissolved faster in etchants than pure silicon

Al-Doped silicon-faster etch rate,

Heavily boron doped-Etch Stop
 Controlled by electrochemical etch stop
 Control Of Wet etching
On etching geometry:
 Timing and agitated flow patterns can affect the geometry of etched

substrate geometry:

 Endurance of the masks is another factor that affects the etching

geometry
Undercutting
Etch Stop by Boron
Doping
Electrochemical Etch
stop
 Dry Etching
 At reduced pressure, a glow discharge is set up in a reactive gas
environment
 This produces ions that can be accelerated by the electric fields at the
bounding edges of the plasma so that they strike the surface –these can
be quite directional in their impact
 Free radicals that can diffuse to the surface and undergo reaction
 Etching depends on reaction followed by creation of a gaseous
byproduct which is pumped away
 Synonyms: plasma etching,
gas etching, physical dry
etching, chemical dry etching,
physical-chemical etching
 Physical Dry Etching
 Physical dry etching requires high energy kinetic energy (ion,
electron, or photon) beams to etch off the substrate atoms.
 When the high energy particles knock out the atoms from the substrate
surface, the material evaporates after leaving the substrate.
 There is no chemical reaction taking place and therefore only the
material that is unmasked will be removed.
 Chemical Dry Etching
 Chemical dry etching (also called vapor phase etching) does not use
liquid chemicals or etchants.
 Involves a chemical reaction between etchant gases to attack the
silicon surface.
 Usually isotropic and exhibits high selectively.
 Ability to etch with finer resolution and higher aspect ratio than
isotropic etching.
 Directional nature of dry etching, undercutting can be avoided.
Tetrafluoromethane (CF4), sulfur hexafluoride (SF6), nitrogen trifluoride (NF3),
chlorine gas (Cl2), or fluorine (F2)
 Reactive Ion Etching
 Reactive ion etching (RIE) uses both physical and chemical
mechanisms to achieve high levels of resolution.
 Most diverse and most widely used processes in industry and research.
 The high energy collision from the ionization helps to dissociate the
etchant molecules into more reactive species
 Cations are produced from reactive gases which are accelerated with
high energy to the substrate and chemically react with the silicon.
 RIE gases- CF4, SF6 and BCl2 + Cl2
 Multi-level Etching
 Making multi level etches can be challenging
 For through etches with two different depths, simply etch from both
sides of the wafer, with double-sided alignment
 DRIE
Working principle:

The DRIE process provides thin films of a

few microns protective coatings on the
sidewalls during the etching process.

 It involves the use of a high-density plasma

source.

The process allows alternating process of

plasma (ion) etching of the substrate
material and the deposition of etching-
protective material on the sidewalls.

Special polymers are frequently used for

side-wall protective films.
Wet Vs Dry Etch
Microneedle
Problems in lithography
 Though the concept of photolithography is simple
 actual implementation is very complex and expensive.

 This is because

(1) nanostructures significantly smaller than 100 nm are difficult to

produce due to diffraction effects,
(2) Masks need to be perfectly aligned with the pattern on the wafer,
(3) The density of defects needs to be carefully controlled, and
(4) Photolithographic tools are very costly, ranging in price from tens to
hundreds of millions of dollars.
Electron-beam lithography
 Electron-beam lithography and X-ray lithography techniques have been
developed as alternatives to photolithography.

 In the case of electron beam lithography, the pattern is written in a

polymer film with a beam of electrons. Since diffraction effects are
largely reduced due to the wavelength of electrons, there is no blurring
of features, and thus the resolution is greatly improved.
However, the electron beam technique is very expensive and very slow.
 In the case of X-ray lithography, diffraction effects are also minimized
due to the short wavelength of X-rays, but conventional lenses are not
capable of focusing X-rays and the radiation damages most of the
materials used for masks and lenses.
Soft Lithography
 Soft lithography
Soft lithography opportunity assessment

“Soft” means no energetic

particles (electron, ions) or
radiation (UVs, X-ray) is involved.
Instead, soft elastomeric stamp is
Soft lithography:
used.
Low cost
Molding, printing or transferring
Resolution usually not very high
Application in microfluidic, biomedical …

George M. Whitesides (Harvard)

s not the only thing that matters, function is more important” (something like this), Whites
 PDMS: poly(dimethyl-siloxane)

PDMS properties:
• Silicone elastomer with a range of viscosities
• Flexible (1 MPa Young’s modulus, typical polymer 1 GPa) and
easy to mold.
• Elastomer, conforms to surface over large areas.
• Chemically inert, optically transparent
• Low surface energy: bonds reversibly (or permanent).
• Seals to flat and clean surfaces for micro-fluidic channels
• Durable (reusable), low thermal expansion
• Biocompatible (even used for food additive)
• Environmentally safe
• Best Resolution: 2-10 nm (for hard PMDS)

Dow Corning brand

84
 PDMS surface treatment

Upon treatment in oxygen plasma,

PDMS seals to itself, glass, silicon,
silicon nitride, and some plastic
materials.

Plasma
oxidation

Air (10 min)

contact PDMS surfaces

Irreversible seal:
formation of covalent
bonds

Biggest issue: it becomes hydrophobic quickly, very bad for micro-fluidic

applications.
(liquid hard to get into the channels once it becomes hydrophobic)
PMDS is absolutely the most popular material for bio-medical lab-on-chip
 PDMS surface treatment

• PDMS has a low interfacial free energy such that molecules of most
polymers won’t stick on or react with its surface.
• The interfacial free energy can be manipulated with plasma treatment.
• For nano-imprint or soft lithography mold, plasma can make PMDS surface
like SiO2, easy for mold release agent coating using silane chemistry.
 PDMS fabrication

Cure on hotplate for few hours

Peel off PDMS

Master pattern (red color) can be in: photoresist (SU-8), silicon,

glass…
Silanization of master mold needed to obtain low surface energy 87
 Microfabrication of
Microgrooved Patterns
UV exposure
Chrome mask
Development

Photoresist
Si wafer
PDMS
polymerization

Stamp peeled out

SEM image
 Micro fabrication & Replica
Molding
mask Expose Cast PDMS
& Develop PDMS Drill & Seal

photoresist master
on Si wafer

inlets outlet

flow

Side View
finished 1 cm
device
 The most recent
lithography methods
Printing, stamping, and molding use mechanical processes instead of photons or
electrons. These methods are normally called soft lithography
methods because they involve the use of polymers.
microcontact printing method
A chemical precursor to polydimethylfiloxane
(PDMS) is poured over and cured into the rubbery
solid PDMS stamp that reproduces the original
pattern. The stamp can then be used in various
inexpensive ways to make nanostructures.
The stamp is inked with a solution consisting of
organic molecules and then pressed into a thin film
of gold on a silicon plate.
The organic molecules form a self-assembled
monolayer on the solid surface that reproduces the
pattern with a precision of approximately 50 nm.
 Advantages of lithography
Once the master template has
been made, no special equipment
is required.
Soft lithographic methods are
capable of producing nanostructures in a wide
range of materials and can
print or mold on curved as well as
planar surfaces

Photolithography. A beam of UV light activates

the photoresist, transferring the pattern
fromthe mask to the sample.
Nanosphere lithography
Micromachining methods
 Focused ion-beam (FIB) machining
FIB machining offers the greatest resolution, with the
ability to make features as small as 20 nm, but it is very
slow.
In FIB a beam of gallium ions from a liquid metal ion
source is accelerated, filtered, and focused with
electromagnetic lenses to give a spot size of 5–8 nm.
The beam is tracked across the surface, contained in a
chamber under high vacuum. The high-energy ions blast
atoms from the surface, allowing simple cutting of slots
and channels or the creation of more elaborate 3-D
shapes. Secondary electrons are emitted when the gallium
ions displace the surface atoms. These can be used to
image the surface, allowing observation and control of the
process as it takes place.
Dual-beam FIBs have an additional electron gunthat is
used as an alternative way of imaging. The precision is
extraordinary.
 MEMS as diagnostics
tool
 The MEMS device used for many
diagnostic tools is the chemical
sensor array (CSA). These
devices are used for disease
identification, for gathering the
biomolecular information needed
to prescribe appropriate drugs for
personalized medicine, and
antibody identification

 CSA are found in many lab-on-a-

chip (LOC) devices.
Chemical Sensor Arrays (Can detect,
identify and determine the amount of an
analyte in solution for the purpose of
diagnosis)
 Lab-on-a-chip
Sampling Pre-treatment Reaction Analysis Data handling

Reagents Waste

Sample
 Lab-on-a-chip

 Microfluidics are integrated microchips that allow separations, chemical

reactions, and calibration-free measurements to be directly performed with
minute quantities of complex samples (blood, environmental gases).
 Microfluidics applications are used in remote locations for clinical
diagnostics and environmental sensing.
 Lab-on-a-Chip (LOC) systems enable the design of small, portable, rugged,
low-cost, easy to use, yet extremely versatile and capable diagnostic
instruments.
 Micro fabrication & Replica
Molding
mask Expose Cast PDMS
& Develop PDMS Drill & Seal

photoresist master
on Si wafer

inlets outlet

flow

Side View
finished 1 cm
device
 Lab-on-a-chip
 Microfluidics involve movement, mixing and control of small volumes
(nanoliters) of fluids.

 A typical microfluidic system is comprised of needles, channels, valves,

pumps, mixers, filters, sensors, reservoirs, and dispensers.

 Microfluidics enable bedside or at the point-of-care (POC) medical

diagnosis.

 A POC diagnostic microfluidic system uses bodily fluids (saliva, blood, or

urine samples) to perform sample preconditioning, sample fractionation,
signal amplification, anlyte detection, data analysis, and result display.
 Cell Culture

 MEMS Cell Culture Array. This array creates a microenvironment for

growing cells in vitro and in parallel, allowing for the analysis of multiple cell
growth conditions. A diagram of how it works is on the left. The constructed
array is shown with a scanning electron microscope (SEM) image on the right.
 Two inlet device

Normalized Fluorescence Intensity

1.0
FITC- dextran
Fluorescein-Na+ salt
0.8

0.6

B
A Inlets
0.4

0.2

Microfluidic
0.0
Diffusion 0.0 0.2 0.4 0.6 0.8 1.0
Diluter ( µDD) Normalized Position

Cell Culture a b c d e f g h i j
Compartments Fluorescein-Na+ salt

FITC- dextran

2
Outlet C 3

Schematic illustration and initial characterization of a multicompartmented microfluidic device. (A) The microfluidic network
design consists of an upstream microfluidic diffusion diluter (µDD) and downstream cell culture compartments. The device was
assembled by making irreversible contact between PDMS replica embossed with desired surface pattern and glass substrate.
(B) Fluorescence intensity profile taken across the main wide channel (5 mm long, 1 mm wide, and 0.1 mm high) of the µDD using
0 and 10 µM fluorescein-Na+ salt (for estimation of gradient cadmium ions concentrations); whereas, 0 and 1 µM FITC-dextran
(150 kD) are used for the estimation of gradient QDs concentrations. (C) Micrographs of cell culture compartments and the
representative fluorescent images are shown.
 Morphological effects

A a b c d e f g h i j

B a b c d e f g h i j

C a b c d e f g h i j

Morphological effects of CdCl2 and QDs in BALB/3T3 cells. DIC images of cultured BALB/3T3 fibroblast cells
treated with gradient flow of growth media containing (A) 0 and 50 µM cadmium chloride (a and j,
respectively), (B) 0 and 1 nM MPA-coated CdSe/ZnSe QDs (a and j, respectively), (C) 0 and 0.04 nM
CTAB/TOPO-coated CdSe/ZnSe QDs ((a and j, respectively) for 12 h. Optical images were captured from
representative compartments after completion of the treatment. Morphological changes depict characteristic
features of apoptosis such as cell shrinkage and membrane blebbing in case of cells treated with cadmium
and CTAB-coated QDs . Data shown are representative of three independent experiments. Scale bars: 100
µm.