Lecture four

Surface modification

- Despite the advent of advanced manufacturing tools and newly

developed materials with unique properties, why is the attention of
biomedical scientists and engineers focused on biomaterial surfaces?

- The material’s surface governs tissue–biomaterial interactions and these

usually occur within a narrow depth of less than 1 nm on the material’s
surface. Surface modification of biomaterials allows the tailoring of
surface properties without affecting bulk material properties. These altered
surface properties influence tissue–biomaterial interactions, which
ultimately determine the success or failure of a device placed in the human
body. In addition to improving tissue–biomaterial interactions,
modification of biomaterial surfaces may also be performed for the purpose
of improving surface mechanical properties such as wear resistance. This
can be achieved through surface or subsurface alloying, or heat treatment.
Enhancement of surface oxide thickness or the presence of a dense
protective coating on a metallic surface can provide surface barriers which
minimize the metal’s chemical reactions with its surroundings, thereby
improving its corrosion resistance. Thus, through surface modification, the
native surfaces of biomaterials can be physically or chemically
transformed with the primary goal of engineering desired surface
chemistry, topography, reactivity, biocompatibility or hydrophilicity.

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_ Surface modification is employed to modify surface properties, with
minimal effect on bulk properties.
_ The parameters used in the surface modification processes significantly
impact how surface properties are altered.

Since surface modification for medical implants is primarily used to

improve or optimize the properties of a biomaterial, the various
modification techniques should generally be simple, robust, and cost
effective so as to promote their inclusion in the manufacturing process.
These techniques may include passivation, anodization, etching,
deposition of coatings, and sterilization. Although there are many different
approaches to engineering biomaterial surfaces,

- What is classification of surface modification techniques

- most surface modification techniques can generally be classified into two
categories, namely
_ subtractive modifications, and
_ additive modifications.
Subtractive surface modifications refer to a change in the surface as a result
of removal of the surface layer. Such modifications are also known as
physical modifications. Means to achieve subtractive surface modification
include abrasive blasting and plasma treatments. In contrast, additive
surface modifications refer to a change in the surface as a result of
depositing films or biological factors on the biomaterial surface. Also
known as over-coating or chemical modifications, common methods for
achieving additive surface modifications include physical and chemical
vapor deposition, grafting, attachment of self-assembly molecules, and
layer-by-layer deposition.

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-With any modification process, what is important parameters used
for altering biomaterial surfaces
-it is important to note that the parameters used for altering biomaterial
surfaces, such as gas used, voltage, current density, environmental
pressure, and temperature, play important roles in governing the chemical,
structural, and mechanical properties of the surface and near-surface.
Surface properties altered could include chemistry, grain size,
crystallographic orientation, defects, stress concentration, film adhesion,
surface topography, and biology–biomaterials interactions.

1. Plasma glow discharge treatments

Generally, the plasma glow discharge treatments used in the field of
biomaterials are mainly for the chemical and physical alterations of surface
compositions and microstructures.
A simple glow discharge chamber or cell can be made by inserting a
cathode and an anode in the cell or by having the walls of the cell act as
these electrodes. Typically, the material to be modified acts as the cathode.
An inert or a reactive gas at pressures ranging from a few mTorr to
atmospheric pressure is then used to fill up the cell or chamber. Ionization
of atoms occurs when a potential difference is applied between the two
electrodes, resulting in gas breakdown and yielding free electrons and
positively charged ions. The positively charged ions move towards and
bombard the cathode, thereby resulting in the release of electrons, called
secondary electron emission. In contrast, electrons arrive in the plasma and
collide with gas particles, thereby resulting in ionizing and exciting the gas
particles. In the absence of an outside excitation source, the gas molecules
in a glow discharge chamber are electrically neutral.
In the application of an outside excitation source between the two
electrodes, such as an electric current or via intermolecular interactions or
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collisions with one another at high temperatures, plasma is created when
the atoms or gas molecules gain enough energy. Ionization occurs,
resulting in the physical removal of electrons from an atom or molecule in
the gaseous state at low pressure and these free electrons are accelerated
toward the anode. As a result of the electron’s low mass, these free
electrons rapidly achieve high velocity or kinetic energy. Since kinetic
energy can be related to temperature, the electrons are also said to have
achieved extremely high temperatures rapidly in a cell filled with reactive
or inert gas molecules. As a result of the high kinetic energy, these
electrons are “hot,” and the high electron temperature results in the need
for inelastic electron collisions in order to sustain the plasma. Gas
molecules such as argon have high mass. Having an atomic weight of
39.948 amu, argon moves slowly towards the cathode. These slow-moving
gas molecules are also termed “cold” gas molecules. Very little of the
electron’s energy is depleted during elastic collisions between the electron
and gas molecules. As a result of the great mass difference between the gas
molecules and electrons, gas molecules are not significantly influenced by
elastic collisions. However, during inelastic collisions of the electrons and
the gas molecules, two primary events can occur in the cell or chamber.

- Ionization: this results in the production of positive ions and electrons,

and
- excitation or elevation of energy level of the gas molecules: the excitation
state is usually short-lived and the excited molecules returned to the state
with the lower energy level as a result of decay or relaxation. The
excitation–decay process of the gas molecules is thus responsible for
characteristic light of the glow discharge.

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- What are two different types of gas discharge plasma
- There are two different types of gas discharge plasma, namely the local
thermal equilibrium (LTE), and the non-LTE. In LTE plasma, all plasma
species in localized areas are in thermal equilibrium, that is, they exhibit
similar temperatures This equilibrium in temperature is a result of high
pressure or multiple collisions in the plasma, thereby providing an efficient
energy exchange or transfer between the plasma species. Applications for
LTE plasma discharge include cutting, welding, spraying, or analytical
analysis where high temperature is required. In contrast, for the non-LTE
plasma, the different plasma species in localized areas of the plasma are
not in thermal equilibrium and exhibit dissimilar temperatures. The non-
LTE plasma is achieved at low gas pressure or few collisions in the plasma,
thereby leading to inefficient energy transfer or exchange between the
plasma species. Applications of non-LTE plasma discharge include
deposition of layers or etching where high temperatures are not required.

1.1 Direct current glow discharge

When the outside excitation source is a direct current (d.c.), the plasma is
created when a potential difference of a few hundred volts to a few
kilovolts is applied between the two electrodes. As shown schematically in
Figure 1.1, the application of the potential difference results in the emission
and the acceleration of electrons from the cathode towards the anode.
On the way to the anode, the accelerated electrons collide with the gas
atoms or molecules. Through these collisions, a plasma is formed when
electrons are forced out of the neutral gas molecules, thereby resulting in
the production of ion pairs consisting of the resultant positive ion and
detached negative electron. Some electrons are attached to the neutral gas
molecules forming negative ions. As such, the plasma formed will consist

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of equal concentrations of positive and negative ions as well as a large
number of neutral gas molecules.

Figure 1.1 Schematic showing the basic ionization process in a d.c. glow discharge:
e = electrons; G= gas molecules, G = positive ions. Arrows indicate direction of flow
of ions.

Additionally, the plasma created is self-sustaining. This is because the

positively charged ions created by the ionization collisions accelerate
toward the cathode or the negatively biased sample surface. Also known as
cathodic sputtering, these positively charged ions strike the sample surface
with sufficient energy, disrupting atomic bonds, ejecting atoms and
releasing secondary electrons. These secondary electrons are accelerated
away from the cathode, resulting in more ionization collisions. As a result
of the various collision processes, the plasma can contain several kinds of
radicals and excited species, in addition to positive and negative ions,
electrons, and neutral gas molecules or atoms. The interactions of these
different species thus make the glow discharge plasma a complicated gas
mixture.
In a d.c. glow discharge, the application of a continuous potential
difference between the cathode and the anode results in a constant current.

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Problems with the d.c. glow discharge can include the following.
_ The inability to use a non-conducting electrode in the chamber or cell.
Since no current will flow through a non-conductive material, the use of a
non-conductive electrode or having non-conductive samples as one of the
electrode leads to a short breakdown, followed by the creation of a surface
charge when d.c. voltage is applied.
_ Buildup of the electrons due to the constant current, thereby resulting in
the burn-out of the glow discharge.

1.2 Alternating current glow discharge

To overcome the problems of the d.c. glow discharge, magnetic fields and
alternating current (a.c.) are some of the commonly used excitation sources
for the ionization process. The application of magnetic fields, as in the
magnetron glow discharge, allows electrons to circulate in helices around
the magnetic field lines, thereby increasing ionization. The application of
a.c. causes a time-varying potential difference, thereby resulting in short
consecutive discharges. During these short discharges, the two electrodes
alternatively play the role of the cathode and the anode, with electrons
oscillating in the plasma between the electrodes.
Since materials used for medical devices can be non-conductive or
conductive, the RF glow discharge is commonly used as one of methods
for modifying biomaterials surfaces, with typical frequencies of a.c.
voltages applied in the RF range of 1 kHz to 103 MHz. Clean, surface-
activated surfaces, with thinner and more stable oxide films are produced
on metallic biomaterials surfaces with RF glow discharge. There are two
general types of RF glow discharge, namely the capacitively coupled RF
glow discharge and the inductively coupled RF glow discharge.

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2. Physical vapor deposition (PVD)
Physical vapor deposition (PVD) is a general term that refers to a family
of vaporization coating techniques for depositing thin films on substrates.
Like the thermal spraying process, PVD is a line-of-sight process in a
vacuum chamber involving the pure physical transfer of material at the
atomic level. In general, the four steps involved in PVD are
_ evaporation,
_ transportation,
_ reaction, and
_ deposition.
During evaporation, a target making up the material to be deposited is
converted into vapor by physical means such as beams of accelerated, high-
energy electrons or ions. The bombardment of these high-energy electrons
or ions onto target materials causes surface atoms from the target to be
dislodged with sufficient energy. The energized, dislodged atoms from the
target are then transported to the substrate surfaces in a straight line.
Depending on the gas used in the PVD, the dislodged atoms may react with
reactive gases such as oxygen, nitrogen, and methane during the
transportation process. No reactions occur if a noble gas is used.
Deposition is said to occur when the atoms are deposited on the substrate
surface and build a coating layer.
A number of different PVD systems are currently used either in
engineering research or commercially for modifying medical device
surfaces. These different PVD systems used include
_ evaporative deposition,
_ pulsed laser deposition, and
_ sputter deposition.

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2.1 Sputter deposition
Thin films can also be deposited by using the sputtering deposition process,
illustrated in Figure 1.2. Like evaporative deposition, sputter deposition is
performed in a vacuum environment at room temperature. In general,
sputtering involves the erosion of a target material from its surface. The
eroded target material is largely driven by momentum exchange as a result
of collisions between atoms from the target surface and high-energy
gaseous ions generated using a plasma or a separate ion beam source. The
gaseous ions,
accelerated by high voltage, bombard and collide with atoms on the target
surface. As a result, the atoms, or occasionally entire molecules, of the
target material are then ejected and transported to the substrate surface,
resulting in a thin film that forms mechanical interlocking and chemical
bonding with the substrate. Several sputtering modes for depositing thin
films exist and the selection of a sputter mode is dependent on the electrical
conductivity of the target material.

Figure 1.2 Schematic of a sputter deposition process under high vacuum. Ions are
observed to strike the target surface, thereby allowing the erosion of the eroded target
materials to be deposited on the substrate surface.

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2.2 Evaporative deposition
For evaporative deposition to occur, the target material must be evaporated
and condensed onto the substrate surface. Under high vacuum, the target
material is melted using an electric resistance heater. A schematic of
evaporative deposition is shown in Figure 1.3.

Figure 9.12
Figure 1.3 Schematic of experimental set up for evaporative deposition under high
vacuum. The arrow indicates the direction of vapor flow towards the substrate.

2.3 Pulsed laser deposition

Another type of PVD is the pulsed laser deposition process. Pulsed laser
deposition requires a highly focused, power pulsed laser beam to strike a
target material in a vacuum chamber filled with a gas such as argon or
oxygen. A schematic of the pulsed laser deposition process is shown in
Figure 1.4. Penetration of the laser pulse into the surface of the target
results in electronic excitation of the target due to the removal of electrons
from its atoms. Oscillating within the electromagnetic field of the laser,
these free electrons collide with target atoms as well as the gas atoms in
the chamber.

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Figure 1.4 Schematic of pulsed laser deposition process under high vacuum. The arrow
represents a highly focused laser beam from a laser source striking the target during the
process

The collision of electrons with the gas induces the formation of plasma in
the chamber through ionization and excitation of the gas molecules,
whereas the collision of electrons with the target heats up the target surface,
thereby resulting in vaporization and expansion of the target material
content in the plasma. As in other deposition processes, the addition of
target materials in the plasma results in the acceleration of these materials
and the eventual bombardment of the substrate surfaces with these target
materials. As a result, deposition of the target material and cleaning of the
substrate surfaces occur simultaneously. A collision region within the
plasma plume is consequently formed where species from the
substrate that are emitted as a resulting of cleaning, collide with the arriving
target materials, thereby generating a condensation of particles. A thermal
equilibrium is achieved when the condensation rate is sufficiently high to

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result in a net deposition of target materials on substrate surfaces as thin
films. Factors affecting the thickness
of the deposited film include
_ composition of the target material,
_ energy of the laser beam,
_ distance between the target and the substrate, and
_ gas used in the vacuum chamber.

3. Chemical vapor deposition (CVD)

Although use of chemical vapor deposition (CVD) has many applications
in a wide range of industries such as in the fabrication of semiconductor
devices and the production of ceramic matrix composites, CVD can also
be used for surface modification in the biomedical arena. For biomaterials,
CVD can be utilized to produce diamond and diamond-like carbon (DLC)
coatings. In general, CVD is an extremely versatile process that can be used
for depositing almost any metallic or ceramic compound. Unlike PVD
which is a pure physical deposition process requiring a high temperature,
the generation of a plasma plume, and the bombardment of ions on the
target surface, CVD is a chemical process using thermal energy to heat up
the gases in the coating chamber and drive the deposition reaction. The
temperature during the CVD process is at least 1000 _C. Like PVD, which
consists of four general steps in the deposition process, the CVD process
consists of the following five general steps.
_ Introduction of gas reactants into the vacuum or reaction chamber at
room temperature.
The gas reactants contain mixtures of precursor gases and a carrier gas.
_ Moving of gas reactants toward the heated substrates.
_ Absorbing of the gas reactants on the heated substrate surfaces.

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_ High temperature of the heated substrates allowing for chemical reactions
of gas reactants to form a coating.
_ Desorption and evacuation of gaseous by-products from the reaction
chamber.

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