MODULE 3

Materials for MEMS- Silicon – Silicon compounds – Silicon Nitride , Silicon

Dioxide , silicon carbide , Poly Silicon, GaAs, Silicon Piezo Resistors,
Polymers in MEMS – SU-8, PMMA, PDMS, Langmuir – Boldgett Films.

MATERIALS FOR MEMS

SILICON

Silicon – an ideal substrate material for MEMS

. Silicon (Si) is 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 .
(2) Silicon is almost an ideal structure material. It has about the same Young’s modulus as
steel (∼ 2x105MPa), but is as light as aluminum with a density of about 2.3 g/cm3. Materials
with high Young’s modulus maintain a linear relationship between applied load and the
induced deformations.
(3) 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.
(4) Its thermal expansion coefficient is about 8 times smaller than that of steel, and is more
than 10 times smaller than that of aluminum.
(5) Silicon shows virtually no mechanical hysteresis. It is thus an ideal candidate material
for sensors and actuators.
(6) Silicon wafers are extremely flat for coatings and additional thin film layers for building
microstructural geometry or conducting electricity
(7) 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.
 MODULE 3

The most commonly used method for producing pure silicon in a single crystal is the
Czochralski (CZ) method.

Fig: Czochralski method for growing single crystals

The raw Silicon, in the form of quartzite are melted in a quartz crucible, with carbon
(coal, coke, wood chips etc). The crucible is placed in a high temperature furnace. A seed
crystal, which is attached at the tip of a puller, is brought into contact with the molten Si to form
a larger crystal. The puller is slowly pulled up along with a continuous deposition of silicon melt
onto the seed crystal. As the puller is pulled up, the deposited silicon melt condenses and a large
bologna- shaped boule of single crystal is formed. The diameters of the boules vary from 100
mm to 300 mm.

Principal materials in the silicon melt are silicon oxide and silicon carbide. These materials
react at high temperature to produce pure silicon, along with other gaseous by-products

SiC + SiO2 → Si + CO + SiO

The gases produced by the above reaction escape to the atmosphere and the liquid Si is left
and solidifies to pure silicon.
Single silicon crystal structure
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)

Three principal uses of Silicon oxide in microsystems are

1) as a thermal and electric insulator

2) as a mask in the etching of silicon substrates

3) as a sacrificial layer in surface micromachining.

Silicon oxide has much stronger resistance to most etchants than silicon. Silicon dioxide
can be produced by heating silicon in oxidant such as oxygen with or without steam

Si + O2 → SiO2 for dry oxidation

Here Si is treated with dry oxygen to get SiO2

 Si + 2H2O → SiO2 + 2H2 for wet oxidation in steam
Here Si is treated with wet steam at high temperature to get SiO2 and hydrogen as biproduct.

Silicon carbide (SiC)

 The principal advantage is its superior dimensional stability and chemical stability at high
temperature.
 It has a high melting point and has a very strong resistance to oxidation even at very high
temperature. This property make SiC an ideal candidate for being masks in micro
fabricationprocesses.
o Thin films of SiC are deposited over the MEMS components to protect them from
extreme temperature. Attraction of using SiC in MEMS is that dry etching with
aluminium masks can easily pattern the thin SiC film. The patterened SiC film can
be used as a passivation (protective) layer in micromachining for the underlying Si
substrate, as SiC can resist common etchants, such as KOH and HF. SiC is a by-
product in the process of producing single crystal silicon boules. As silicon exists
in the raw materials of carbon (coal, coke, woodchips), the intense heating of
these materials in the electric arc furnace results in SiC sinking to the bottom of
the crucible.

Silicon Nitride (Si3N4)

 It provides an excellent barrier to diffusion to water and ions.

 Its ultra-strong resistance to oxidation and many etchants makes it suitable in a mask for
deep etchings.
 It is used in high strength electric insulators and ion implantation masks.
 Application of silicon nitride include optical waveguides, encapsulates to prevent diffusion
of water and other toxic fluids into the substrate.
 It is produced by chemical reaction:

3SiCl2H2 + 4NH3 → Si3N4 + 6HCL + 6H2.

 Polycrystalline silicon/ Poly Silicon

 Silicon in polycrystalline form can be deposited onto silicon substrates by chemical vapour
deposition. The low pressure chemical vapour deposition (LPCVD) process is frequently used
for depositing polycrystalline silicon onto silicon substrates. It occurs at 6000C-6500C.

Polysilicon deposit on Si substrate

 These polysilicon usually are highly doped silicon.

 Multiple layers of pure silicon crystals. Each layer will have different orientations.
 It is an aggregation of pure silicon crystal with randomly orientations deposited on the top of
silicon substrates.
 They are deposited to the substrate surfaces to produce localized resistors, gates for transistors,
thin film transistors etc.
 Being randomly oriented, polysilicon is even stronger than single silicon crystals.
 Highly doped polysilicon can reduce the resistivity of polysilicon to produce conductors and
control switches. They are thus ideal materials for microresistors as well as ohmic contacts.

Gallium Arsenide (GaAs)

 GaAs is a compound semiconductor with equal number of Ga and As atoms.

 Because it is a compound,it is more complicated in lattice structure & more difficult
toprocess.
 It is an excellent material for monolithic integration of electronic and photonic devices on a
single substrate.
 The reason for being excellent material for photo electronics is its high electron mobility (7
times more mobile than silicon). The high electron mobility makes current flow easier.
 GaAs is also a good thermal insulator with excellent dimensional stability at high
temperature.
 GaAs is less attractive as a substrate in microsystems as its yield strength is low ( one third
of silicon).
 It is more expensive than silicon.

Silicon Piezo resistors

Piezo resistance is defined as a change in electrical resistance of solids when subjected to
stress fields. Doped silicon are Piezo resistors p-type or n-type.
 Silicon piezo resistors having such characteristics are widely used in micro sensors and
actuators. Relationship between change of resistance {∆R} and stresses {σ} is

{∆R} = [π] {σ}

where {∆R} = { ∆Rxx ∆Ryy ∆Rzz ∆Rxy ∆Rxz ∆Ryz}T represents the change of resistances in an
infinitesimally small cubic piezo resistive crystal element with corresponding stress components

{σ} = {σxx σyy σzz σxy σxz σyz}T and [π] = piezo resistive coefficient matrix.

Due to equilibrium condition, there are six independent stress components: 3 normal stress
components and 3 shearing stress components. Consequently, the piezoresistive coefficient
matrix has the components

The coefficients π11 and π12 associated are associated with normal stresses and π44 is related to
shearing stress.

In MEMS and Microsystems, silicon piezoresistors exist in the form of thin strips. Here
only the in-plane stresses in the x and y directions are considered. The value of 𝜋𝐿denote the
piezoresistive coefficient along the longitudinal direction, i.e along <x> direction, whereas 𝜋𝑇
represents piezoresistive coefficient in the tangential direction, i.e along <y> direction.

The change of electric resistance in a silicon piezoresistance gage is:

where ΔR and R represents the change of resistance and the original resistance of the silicon
piezoresistive respectively. The value of R can be obtained either by direct measurement or by
formula
𝜌𝑙
𝑅=
𝐴
where 𝜌 is the resistivity of the piezoresistor, L the length and A the area of piezoresistor. The
stress components in the longitudinal and tangential directions, σL and σT are the stresses that
causes the change of the resistance in the piezoresistor.

A major drawback of silicon piezoresistors is the strong temperature dependence of their

piezoresistivity. The sensitivity of piezoresistivity to the applied stress decreases rapidly with
increase of temperature.

POLYMERS IN MEMS
Characteristics of Polymers
 Low melting point; poor conductivity
 Thermoplastics and thermosets are common industrial products
 Thermoplastics are easier to form into shapes
 Thermosets have higher mechanical strength even at high temperature

Polymers have become important material for MEMS and Microsystems. 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

Demerits associated with polymer materials:

 Visco elastic behavior of polymers is undesirable in certain applications.

 lower glass-transition and melting temperatures
 low thermal stability limits fabrication methods and application potentials.

Some of the applications are:

1. Photoresist polymers are used to produce masks for creating desired patterns on
substrates by photolithography.

2. The same photoresist polymers are used to produce the prime mold with the desired
geometry of MEMS components in the LIGA process for manufacturing microdevice
components
3. Conductive polymers are used as organic substrates for MEMS and microsystems
4. The ferroelectric polymers can be used as a source of actuation in microdevices (for
micropumping)
5. The thin Langmuir-Blodgett (LB) films can be used to produce multilayer
microstructures
6. Polymers with unique characteristics are used as coating substances for capillary tubes to
facilitate electro-osmotic flow in microfluidics.
7. Thin polymer films are used as electric insulators in microdevices and as a dielectric
substances in microcapacitors.
8. Polymers are widely used for electromagnetic interference (EMI) and frequency
 interference (RFI) shielding in microsystems.
9. Polymers are ideal materials for the encapsulation of microsensors and packaging of
other microsystems.
Conductive Polymers
Some polymers can be made electrically conductive by the following 3 methods:
1) Pyrolysis
2) Doping
3) Insertion of conductive fibers
(1) Pyrolysis

(2) Doping
Introducing metal atoms into molecular matrices of polymers→Conductive polymers

(3) Doping Intersection of conductive fibers

Fibers made of Au, Ag, stainless steel, aluminum fibers and flakes

Commonly used MEMS polymers are:

1. Polyimide;
2. SU-8;
3. Liquid crystal polymer;
4. Polydimethylsiloxane;
5. Polymethyl methacrylate (also known as acrylics. plexiglass, or PMMA);
6. Parylene (polyparaxylylene);
7. polytetrafluoroethylene (Teflon) and Cytop.

SU-8

 It is a negative epoxy-based polymer sensitive to UV light(λ=350-400nm)

 used for thin film production with thickness ranging from 1µm to 2mm.
 This was first invented by IBM with the main purpose of allowing high aspect ratio features ( > 15) to
be made in thick photosensitive polymers. The photoresist consists of EPON® Resin SU-8 as a main
component. The EPON resin is dissolved in an organic solvent (GBL, gammabutyrolacton), with the
quantity of solvent determining the viscosity and the range of achievable thickness. Processed layers as
thick as can be achieved, offering new capabilities for masking, molding, and building high aspect ratio
structures at low cost.
 The cost of SU-8 lithography is considerably lower than that of other techniques for realizing high
 aspect ratio microstrucures.
 SU-8 has been integrated in a number of micro devices, including microfluid devices, SPM probes and
micro needles.
 It can also serve as a thick sacrificial layer for surface micromachining.
 It is commercially available in liquid form. SU-8 films can be produced by a spin-process.

Step 1: The Silicon wafer should be dry and clean (using 75% H2SO4 and 25% H2O2 ) prior to being
coated with SU-8 photo resist.

Step 2: The wafer is baked on a flat hot plate at 2000C for 5 min which is then placed on top of a
spinning table. Approximately 1mL per inch of substrate diameter of liquid SU-8 is dispensed onto
the center of the wafer followed by a preset spinning speed according to the desired thickness.
Spinning usually takes about 30s.
Step 3: The wafer with a thin coat of SU-8 is then subjected to a soft bake to drive out the inherent
solvent in the coating. This can be done in a well- vented oven.
Step 4: Exposure to the photo resist is carried out by placing the wafer with a thin SU-8 coating
under a UV lamp with a wave length in the range 350-400 nm. The required photo resist time
relates to the exposure energy by the specific SU-8 supplied.
Step 5: Conditions for post bake are normally specified by suppliers.
Step 6: The exposed photoresist is then ready for development. Solvent for developing SU-8 may
include ethyl lactate and diacetone alchohol or as specified by supplier. The development solvent
removes the parts of SU-8 film that were not exposed to UV light and thereby creates a pattern of
the film over the substrate.
Step 7: After the development the substrate should be rinsed briefly with chemicals such as
isopropyl alcohol and then dried by gentle streams of hot air or inert gas.
Step 8: The developed SU-8 film is then subjected to hard baking for a brief period at moderate
temperature ranging from 150 to 200 deg C on a hot plate with well vent of dry air.
Step 9: Lift off the patterned SU-8 films from the substrates. Depending on the thickness and the
crosslink density of the materials used in the film, several ways are used to remove film from
substrate.

PMMA
PMMA (Polymethyl methacrylate) is a transparent thermoplastic often used in sheet form as a
lightweight or shatter-resistant alternative to glass. PMMA has several alternative names like
acrylic, acrylic glass, plexiglass, acrylate, Lucite, Perspex, etc. The production of PMMA involves
four stages namely, emulsion polymerization, solution polymerization, and bulk polymerization.
It is essentially produced from a compound called propylene, which is obtained by refining
lighter versions of crude oil.The process begins when propylene and benzene react together to form
cumene. The cumene is then oxidized to produce cumene hydroperoxide.Next, the cumene
hydroperoxide is treated with acid to form acetone. The resulting acetone undergoes a three-step
process where it is finally converted into methyl methacrylate. It is supplied in many different
forms, including bulk, sheets, and solutions for spin coating. PMMA bulk, most commonly
known as acrylics, has been used in making microfluidic devices. The photo definable PMMA
thin film is a widely used e-beam and X-ray lithography resist. Spin coated PMMA has been used
as a sacrificial layer.
PDMS
Poly (dimethylsiloxane) (PDMS), an elastomer material belonging to the room
temperature vulcanized (RTV) silicone elastomer family, offers many advantages for general
MEMS applications. It is optically transparent, electrically insulating, mechanically elastic,
gas permeable, and biocompatible. PDMS is widely used in microfluidics. The primary
processing method is molding.
1. The volume of PDMS shrinks during the curing step. Compensation of dimensions at the
design level should be incorporated to yield desired dimensions.
2. Due to volume shrinking and flexibility, deposited metal thin films on cured PDMS tends to
develop cracks, affecting the electrical conductivity.
3. The surface chemical properties (such as adhesion energy) can be varied by altering the
mixing ratio and through surface chemical or electrical treatment.

PDMS is commercially supplied as a viscous liquid—it can be cast or spin coated on

substrates. PDMS material is not photo definable. It therefore cannot be simply spin-coated and
patterned like photosensitive resists. It is possible to use plasma etching to pattern PDMS thin
films. However, the etch rate is rather slow. The measured etch rate is approximately 7 nm/min
at 800 W power and 100 V bias. Etching of PDMS with O 2 plasma leaves the surface and line
edges rough.

Langmuir-Blodgett (LB) films

The process of producing thin polymer films at the molecular scale, was first introduced
by Langmuir in 1917 and was later refined by Blodgett. This process is called Langmuir-
Blodgett process, or LB films. The process involves the spreading volatile solvent over the surface-
active substrate materials. The LB process can produce more than a single monolayer by depositing
films of various compositions onto a substrate to produce a multilayer structure.
Langmuir-Blodgett process
The main idea of the method is to form a monomolecular layer of an amphiphilic
substance on the water surface and then transfer it to a solid substrate. In the aqueous phase the
amphiphilic substance molecules are arranged on the air-water interface. To form a
monomolecular surface layer the surface layer is compressed using a special barrier (Fig 1). The
sequential isothermal compression changes the structure of the monomolecular film, which
passes through a series of two-dimensional states, conventionally referred to as gas, liquid crystal
and solid crystal (Fig. 2). Thus, knowing the phase diagram of the film one can control its
structure and associated physico- chemical properties. To transfer the film to a solid support, a
flat substrate is immersed in the solution and then extracted with the surface film adsorbed on it.
The process of monomolecular film transfer can be repeated many times to obtain various multi
molecular layers.

Fig. 1. Schematic diagram of Langmuir-Blodgett films making.

Fig. 2. Condition of Langmuir-Blodgett film depending on the surface pressure

Advantages
LB films are good candidate materials for exhibiting ferro (magnetic) , pyro (heat-
generating) and piezoelectric properties. LB films may also be produced with controlled optical
properties such as refractive index and anti reflectivity. They are thus ideal materials for micro
sensors and optoelectronic devices.
Following are a few examples of LB film applications in Microsystems
(1) Ferroelectric (magnetic) polymer thin films:
Applications of this type of films include: - Sound transducers in air and water, Tactile
sensors, Biomedical applications such as tissue compatibility implants, cardio- pulmonary
sensors and implantable transducers and sensors for prosthetics and rehabilitation devices.
(2) Coating materials with controllable optical properties:
Widely used in broadband optical fibers that transmit laser light at various wavelengths.
(3) Microsensors:
Many electrically conducting polymeric materials are sensitive to the exposed gas and
other environmental conditions. So they are suitable materials for micro sensors. Its ability
of detecting specific substances relies on the reversible and specific absorption of species
of interest on the surface of the polymer layer and the subsequent measurable change of
conductivity of the polymer.

Fig: Microsensor using polymers

In gas sensor, electrical conductivity of the polymer sensing element changes with absorption of
the exposed gas.