Unit 5 – Nanotechnology & Fabrication

Complete Notes: PVD | CVD | Carbon Nanotubes | TEM | SEM | AFM

21PYB102J – Semiconductor Physics and Computational Methods
SRM Institute of Science and Technology | Department of Physics and Nanotechnology
1. Chemical Vapour Deposition (CVD)

1.1 Introduction
Chemical Vapour Deposition (CVD) is a process whereby a solid material is deposited from a vapor by
a chemical reaction occurring on or in the vicinity of a normally heated substrate surface. It is a
commonly used process to deposit thin films on a desired substrate.
CVD involves using volatile precursors that can react or decompose onto a surface, yielding the desired
material. The general reaction is:
Gaseous reactants → Solid material + Gaseous products

1.2 Key Characteristics

• Bottom-up approach to thin film deposition
• Deposited films range from metals to semiconductors to insulators
• High temperatures and low pressures are the most common process conditions
• CVD involves an energy source to break reactant gases into reactive species
• The precursors must be volatile (gaseous) at room temperature — e.g., SiH₄ (Silane) for Silicon
• The Gibbs Free Energy must decrease (ΔG < 0) for the desired reaction to occur
• By-products need to be volatile (gaseous)

1.3 CVD System Components

A typical CVD system consists of the following parts:
• Sources of and feed lines for gases
• Mass flow controllers for metering the gases into the system
• A reaction chamber or reactor
• A system for heating up the wafer on which the film is to be deposited
• Temperature sensors

1.4 CVD Steps (5-Step Process)

• Step 1: Reactants pumped through the reactor
• Step 2: Reactants diffuse across boundary layer to surface of the substrate
• Step 3: Reactants adsorb on surface (chemical or physical)
• Step 4: Surface reactions leading to film formation
• Step 5: Diffusion of by-products away from surface

1.5 Surface Processes

Processes occurring on the surface of the substrate include:
• Adsorption
• Decomposition
• Surface migration
• Chemical reaction
 • Desorption of products

1.6 Reaction Types

Heterogeneous Reactions
Reactions that take place at the substrate surface. These are selective, occurring on the heated surface
of the wafer and creating good-quality films. These are more desirable.

Homogeneous Reactions
Reactions that take place in the gas phase. They form gas phase aggregates of the depositing material,
which adhere to the surface poorly and form low-density films with lots of defects.

1.7 Types of CVD Reactors

Hot-Wall Reactors
Uses a heating system that heats up not only the wafer, but the walls of the reactor itself (e.g., radiant
heating from resistance-heated coils). Films are deposited on the walls too, requiring frequent wall
cleaning.

Cold-Wall Reactors
Minimize heating of reactor walls while the wafer is heated (e.g., via IR lamps inside the reactor).

By Operating Pressure
• APCVD (Atmospheric Pressure CVD): Simplest design, operates at atmospheric pressure
• LPCVD (Low-Pressure CVD): Operates at medium vacuum (30–250 Pa), higher temperatures
• PECVD (Plasma Enhanced CVD): Uses RF-induced glow discharge; operates under low
pressure without depending completely on thermal energy

CVD Advantages Disadvantages Applications

Process
APCVD Simple, Fast Poor Step Coverage, Low-temperature Oxides
Deposition, Low Contamination
Temperature
LPCVD Excellent Purity, High Temperature, Slow High-temp Oxides, Silicon
Uniformity, Good Step Deposition Nitride, Poly-Si, W, WSi₂
Coverage, Large Wafer
Capacity
PECVD Low Temperature, Chemical and Particle Low-temp Insulators over
Good Step Coverage Contamination Metals, Nitride Passivation

1.8 Advantages of CVD

• Can be used for a wide range of metals and ceramics
• Can be used for coatings or freestanding structures
• Fabricates net or near-net complex shapes
• Is self-cleaning — extremely high purity deposits (>99.995% purity)
 • Conforms homogeneously to contours of substrate surface
• Has near-theoretical as-deposited density
• Has controllable thickness and morphology
• Forms alloys and infiltrates fiber preforms and foam structures
• Can simultaneously coat multiple components and coat powders

1.9 Applications of CVD

• Surface modification to prevent or promote adhesion
• Photoresist adhesion for semiconductor wafers
• Silane/substrate adhesion for microarrays (DNA, gene, protein, antibody, tissue)
• MEMS coating to reduce stiction
• BioMEMS and biosensor coating to reduce 'drift' in device performance
• Anti-corrosive coating; Copper capping
• Aircraft and land gas turbine blades, automotive timing chain pins, chemical plant components
2. Physical Vapour Deposition (PVD)

2.1 Introduction
Physical Vapour Deposition (PVD) is fundamentally a vaporisation coating technique, involving transfer
of material on an atomic level. It is an alternative process to electroplating.
The process is similar to CVD except that the raw materials/precursors (the material to be deposited)
start out in solid form, whereas in CVD, the precursors are introduced to the reaction chamber in the
gaseous state.
PVD processes are carried out under vacuum conditions.

2.2 Working Concept — 4-Step Process

Step 1: Evaporation
A target, consisting of the material to be deposited, is bombarded by a high energy source such as a
beam of electrons or ions. This dislodges atoms from the surface of the target, 'vaporising' them.

Step 2: Transportation
This process consists of the movement of 'vaporised' atoms from the target to the substrate to be
coated. It will generally be a straight-line affair.

Step 3: Reaction
In cases where coatings consist of metal oxides, nitrides, carbides and other such materials, the target
consists of the metal. The atoms of metal then react with the appropriate gas during the transport
stage. Reactive gases may be oxygen, nitrogen, and methane. In instances where the coating consists
of the target material alone, this step would not be part of the process.

Step 4: Deposition
This is the process of coating build up on the substrate surface. Depending on the actual process,
some reactions between target materials and reactive gases may also take place at the substrate
surface simultaneously with the deposition process.

2.3 Variants of PVD

• Evaporative Deposition: Material heated to high vapor pressure by electrically resistive heating
in high vacuum
• Electron Beam Physical Vapor Deposition: Material heated to high vapor pressure by electron
bombardment in high vacuum
• Sputter Deposition: Glow plasma discharge (localized around the target by a magnet) bombards
the material, sputtering some away as vapor
• Cathodic Arc Deposition: A high power arc directed at the target material blasts away some into
a vapor
• Pulsed Laser Deposition: A high power laser ablates material from the target into a vapor

Method Merits Demerits

 E-Beam Evaporation High-temp materials, good for liftoff, CMOS radiation sensitivity, alloys
highest purity difficult, poor step coverage
Filament Evaporation Simple to implement, good for liftoff Limited source material, no high-
temp, alloys difficult, poor step
coverage
Sputter Deposition Better step coverage, alloys, high- Possible grainy/porous films, plasma
temp materials, less radiation damage/contamination
damage

2.4 Importance of PVD Coatings

• Improved hardness and wear resistance
• Reduced friction
• Improved oxidation resistance
These coatings improve efficiency through improved performance and longer component life. They may
also allow coated components to operate in environments that the uncoated component would not
otherwise have been able to perform.

2.5 Advantages of PVD

• Materials can be deposited with improved properties compared to the substrate material
• Almost any type of inorganic material can be used, as well as some kinds of organic materials
• The process is more environmentally friendly than processes such as electroplating

2.6 Disadvantages of PVD

• It is a line-of-sight technique — extremely difficult to coat undercuts and similar surface features
• High capital cost
• Some processes operate at high vacuums and temperatures requiring skilled operators
• Processes requiring large amounts of heat require appropriate cooling systems
• The rate of coating deposition is usually quite slow

2.7 Applications of PVD

PVD coatings are generally used to improve hardness, wear resistance and oxidation resistance in
areas such as:
• Aerospace
• Automotive
• Surgical/Medical
• Dies and moulds for all manner of material processing
• Cutting tools
3. Carbon Nanotubes (CNTs)

3.1 Introduction
Carbon nanotubes (CNTs) are allotropes of carbon. These cylindrical carbon molecules have
interesting properties that make them potentially useful in many applications in nanotechnology,
electronics, optics, and other fields of materials science.
They exhibit extraordinary strength and unique electrical properties and are efficient conductors of heat.

3.2 What Are Carbon Nanotubes?

• CNT can be described as a sheet of graphite rolled into a cylinder
• Constructed from hexagonal rings of carbon
• Can have one layer or multiple layers
• Can have caps at the ends making them look like pills

3.3 Discovery
Carbon nanotubes were discovered in 1991 by the Japanese electron microscopist Sumio Iijima who
was studying the material deposited on the cathode during the arc-evaporation synthesis of fullerenes.
He found that the central core of the cathodic deposit contained a variety of closed graphitic structures
including nanoparticles and nanotubes, of a type which had never previously been observed.

3.4 Types of Carbon Nanotubes

Single-Wall Carbon Nanotubes (SWCNTs)
Formed by the rolling of a single layer of graphite into a seamless cylinder. Consist of just one layer of
carbon with a greater tendency to align into ordered bundles. Used to test theory of nanotube
properties.

Multi-Wall Carbon Nanotubes (MWCNTs)

A coaxial assembly of cylinders of SWCNTs, one within another. Consist of 2 or more layers of carbon.
Tend to form unordered clumps. The separation between tubes is about equal to that between the
layers in natural graphite.

3.5 Nanotube Geometry

There are three unique geometries (flavors) of carbon nanotubes:
• Zig-zag (n, 0): Chiral vector passes through mid point of atomic bonding; Chiral angle = 0°
• Armchair (n, n): Chiral vector passes through atoms of six-fold axis; Chiral angle = 30°
• Chiral (n, m): Chiral vector line is not along a mirror line; Chiral angle 0° ≤ θ ≤ 30°, n ≠ m

3.6 Properties of CNTs

Mechanical Properties
• Young's modulus is over 1 Tera Pascal — as stiff as diamond
• Estimated tensile strength is 200 GPa
 • Strength 100 times greater than steel at one-sixth the weight
• Ideal for reinforced composites and Nano Electromechanical Systems (NEMS)
• High strain to failure

Electrical Properties
• Can be superconducting, insulating, semiconducting, or conducting (metallic) depending on
helicity
• Electrical conductivity as high as copper
• CNT with smaller diameter results in increased reactivity

Thermal Properties
• Thermal conductivity as high as diamond

Chemical Reactivity
• Chemical reactivity of a CNT is very high compared with a graphene sheet due to its curved
surface

3.7 Synthesis of CNTs

Arc Discharge Method
A direct current creates a high temperature discharge between two electrodes (carbon is vaporized).
The atmosphere is composed of inert gas at low pressure. Originally used to make C60 fullerenes.
Cobalt is a popular catalyst. Typical yield is 30–90%.
• Advantages: Simple procedure, high quality product, inexpensive
• Disadvantages: Requires further purification, tubes tend to be short with random sizes

Laser Ablation Method

Discovered in 1995 at Rice University. Vaporizes graphite at 1200°C in Helium or Argon gas. A hot
vapor plume forms, expands and cools rapidly. Carbon molecules condense to form large clusters.
Yield of up to 70%.
Types: Pulsed (much higher light intensity ~100 kW/cm²) and Continuous (lower light intensity ~12
kW/cm²).
• Advantages: Good diameter control, few defects, pure product
• Disadvantages: Expensive because of lasers and high-powered equipment

Chemical Vapor Deposition (CVD)

Carbon is in the gas phase. An energy source transfers energy to carbon molecules. Common carbon
gases include Methane, Carbon Monoxide, and Acetylene.

3.8 Applications of CNTs

• Field Emission Transistors: CNT conducting channel results in devices with low power
consumption
• Nanoprobes and Sensors: Used in STM and AFM instruments due to MWNT tips being
conducting; improved resolution over conventional Si or metal tips
• Electronic Devices: Nanotube TVs, nano-wiring
• High Strength Composites: 100 times as strong as steel and 1/6 the weight
• Medical Applications: Encase drugs into nanotube capsules for more predictable time release
• Composite materials: Reinforcements in high strength, low weight, high performance
composites. SWNTs have Young's Modulus of 1 TPa
• Templates: Capillary forces can hold gases and fluids in nanotubes to create nanowires
4. Scanning Electron Microscope (SEM)

4.1 History
The limitation of light microscopes in resolving fine details provided the impetus to develop an electron
microscope in the early twentieth century. The first electron microscope was a transmission electron
microscope (TEM) developed by Max Knoll and Ernst Ruska in Germany in 1931.
German physicist Max Knoll introduced the concept of a scanning electron microscope in 1935.
Another German physicist Manfred von Ardenne elaborated on the principles and produced the earliest
scanning electron microscope in 1937.
The physics behind electron microscopy is based on the Davisson-Germer experiment, which
confirmed that electrons diffract as a wave and verified the de Broglie relation: λ = h/p. Resolution is
directly proportional to wavelength. An electron beam (λ of 0.000004 μm) with an accelerating voltage
of 100 kV can achieve a resolution of 0.24 nm.

4.2 Working Concept

Just like any microscope, the primary function of the SEM is to enlarge small features or objects
otherwise invisible to human sight. It uses an electron beam rather than light. Images are obtained by
scanning a high-energy electron beam on the sample surface.
SEM allows surfaces of objects to be seen in their natural state without staining. The specimen is put
into the vacuum chamber and covered with a thin coating of gold to increase electrical conductivity and
form a less blurred image. The electron beam sweeps across the object, building an image line by line
as in a TV camera. As electrons strike the object, they knock loose showers of electrons captured by a
detector to form the image.
The SEM is one of the most versatile instruments available, with a typical resolution of the order of 10
nm (100 Å) for commercial instruments.

4.3 Working Principle (Step by Step)

• The 'Virtual Source' (electron gun) produces a stream of monochromatic electrons
• The stream is condensed by the first condenser lens, controlled by the 'coarse probe current
knob'
• The condenser aperture eliminates high-angle electrons from the beam
• The second condenser lens forms the electrons into a thin, tight, coherent beam ('fine probe
current knob')
• A set of coils scan or sweep the beam in a grid fashion, dwelling on points for microseconds
• The objective lens (final lens) focuses the scanning beam onto the specimen
• When the beam strikes the sample, interactions occur and are detected by various instruments
• A pixel on a CRT is displayed whose intensity is determined by the number of reactions
• This process is repeated until the grid scan is finished; the entire pattern can be scanned 30
times per second

4.4 Specimen Interactions

Backscattered Electrons
Formation: Caused by an incident electron colliding with an atom in the specimen nearly normal to the
incident's path; the electron is scattered 'backward' 180 degrees.
Utilization: Production varies directly with the specimen's atomic number. Higher atomic number
elements appear brighter. Used to differentiate parts of the specimen with different average atomic
number.

Secondary Electrons
Source: Caused by an incident electron passing near an atom, imparting some energy to a lower
energy electron (usually K-shell). This ionized electron leaves the atom with very small kinetic energy
(5eV) — termed a 'secondary electron'. Each incident electron can produce several secondary
electrons.
Utilization: Very topography related. Only secondaries near the surface (<10 nm) can exit the sample. A
collector with +100V potential attracts secondary electrons to the detector.

Auger Electrons
Source: Caused by de-energization of the specimen atom after a secondary electron is produced. A
higher energy electron from the same atom 'falls' to fill the K-shell vacancy, and the energy surplus is
corrected by emitting an outer (lower energy) electron — an Auger Electron.
Utilization: Have characteristic energy unique to each element. Collected and sorted by energy to give
compositional information.

X-rays
Source: Also caused by de-energization after a secondary electron is produced. As an electron 'falls'
into the lower energy shell, it emits X-rays to balance the total energy of the atom. X-rays have a
characteristic energy unique to the element from which they originated.

4.5 SEM Uses — Information Provided

• Topography: Distribution of features or parts on the surface of a sample
• Composition: What a sample is made of
• Morphology: The form, shape, or structure of a sample

4.6 Strengths of SEM

• A wide variety of specimens can be examined
• Relatively easy and quick sample preparation
• Ease of use due to user-friendly and automated equipment
• Rapid imaging and fast turnaround time
• Relatively straightforward image interpretation
• Large depth of field — ability to focus large depths and produce 3D-like images
• Microchemical analysis capability
• Samples can be dry or wet
• Nondestructive (some beam damage may result)

4.7 Applications of SEM

• Biological Sciences: Identification of bacterial strains, testing vaccines, genetics, climate change
effects on species
• Forensics: Analysing gunshot residue, paint particles and fibres at crime scenes
 • Geological Sampling: Identifying compositional differences of soil and rock samples
• Medical Science: Comparing blood and tissue samples, identifying viruses and diseases, testing
medicines
• Electronics: Microchip assembly, development of new fabrication methods, testing
semiconductors for reliability
• Materials Science: Research into alloys, mesoporous architectures, nanotubes and nanofibres
• Microscopic Quality Control across different industries

4.8 Limitations of SEM

• The sample size is limited
• Samples must be solid
• EDS detector cannot detect H, He, or Li
• Poor detectability limit of elements (with EDS) compared to wet analytical methods
• Samples need to be examined under vacuum
• The instrument typically requires an installation space of 5 × 5 m
• Non-conductive samples need to be coated
5. Transmission Electron Microscope (TEM)

5.1 Working Concept

TEM works much like a slide projector. A projector shines a beam of light through (transmits) the slide;
as the light passes through it is affected by the structures and objects on the slide. These effects result
in only certain parts of the light beam being transmitted through certain parts of the slide. This
transmitted beam is then projected onto the viewing screen, forming an enlarged image.
TEMs work the same way except that they shine a beam of electrons through the specimen. Whatever
part is transmitted is projected onto a phosphor screen for the user to see.

5.2 Common Modes of Operation

• Bright Field (BF) Microscopy
• Dark Field (DF) Microscopy
• Selected Area Diffraction

5.3 Working Principle (Step by Step)

• The 'Virtual Source' (electron gun) produces a stream of monochromatic electrons
• The stream is focused to a small, thin, coherent beam by condenser lenses 1 and 2
• First lens (spot size knob) largely determines the general size range of the final spot
• Second lens (intensity/brightness knob) changes the size of the spot on the sample
• The condenser aperture knocks out high-angle electrons (far from the optic axis)
• The beam strikes the specimen and parts of it are transmitted

5.4 Types of Electrons in TEM

Unscattered Electrons
Incident electrons which get transmitted through the specimen without interacting with the sample.
Utilization: Thicker sample → fewer transmitted electrons → appears darker. Thinner sample → more
transmission → appears brighter.

Elastically Scattered Electrons

Incident electrons which get scattered by the atoms in the sample elastically (no loss of energy), then
transmitted.
Utilization: All electrons follow Bragg's condition for scattering.

Inelastically Scattered Electrons

Incident electrons interact with the sample inelastically (loss of energy) and get transmitted into the
specimen.
Kikuchi Bands: Bands of alternating light and dark lines formed by inelastic scattering interactions,
related to atomic spacing in the specimen.
6. Atomic Force Microscopy (AFM)

6.1 Introduction
The AFM, like the scanning tunneling microscope (STM), is a scanning microscope, but the mechanism
depends on the force of attraction between molecules. The atoms of the tip are attracted to the atoms
of the sample by the van der Waals interaction.
Unlike STM, no current flows between the AFM tip and sample, so the sample need NOT be
conducting. This makes AFM applicable to a much wider range of samples.

6.2 How AFM Works

The AFM tip scans the sample surface. The up and down movement of the tip is recorded by a
position-sensing photodiode. As the AFM tip is attracted to the surface (causing the cantilever to bend),
a laser beam bounces off the end of the cantilever — allowing the tip's movement to be tracked.
As the AFM tip scans the surface, its up and down motions map the contour of the sample — scanned
line by line.

6.3 Force Mechanics

The force on the AFM tip is harmonic (spring-like): the tip is displaced toward the surface a distance (Z)
proportional to the van der Waals force.
• FRestore = Restoring force of cantilever on tip
• FSample = Force of sample pulling on tip (van der Waals)
• FRestore = −kZ, where k ~ 1 N/m
• An AFM can measure forces of pN (10⁻¹² Newton) and even fN (10⁻¹⁵ N)

6.4 Modes of Operation

Contact Mode
The tip is dragged along a sample's surface; the cantilever deflection is measured and translated into
surface shapes.
• Fast scanning, good for rough samples
• But deforms soft samples — can damage the surface

Non-Contact Mode
The cantilever oscillates above the sample's surface and is affected by surface/tip forces (van der
Waals) as it does so.
• Low force exerted on the sample
• Low resolution; contaminant layer can interfere
• Usually needs UHV (Ultra High Vacuum) system for good imaging

Tapping Mode (Intermittent)

The AFM tip taps the sample surface during the closest point of approach of an oscillation cycle.
• Good for biological samples
 • Slow scan speed and challenging in liquids

6.5 Advantages of AFM

• Provides a true three-dimensional surface profile (unlike SEM which gives 2D projection)
• Samples viewed by AFM do not require any special treatments (such as metal/carbon coatings)
• Most AFM modes can work in ambient air or even a liquid environment — enabling study of
biological macromolecules and living organisms
• Can provide higher resolution than SEM; true atomic resolution in ultra-high vacuum (UHV)
• Does not require a conducting sample
• Used to study a variety of samples

6.6 Disadvantages of AFM

• Image size is limited — can only image a maximum height on the order of micrometers and a
maximum scanning area of around 150 × 150 micrometers
• SEM can image an area of millimeters by millimeters — much larger than AFM
• At high resolution, image quality is limited by the radius of curvature of the probe tip
• Incorrect choice of tip for the required resolution can lead to image artifacts
• Slow scan and less scanner area
• Tip Convolution: Does not reflect the true sample topography but represents the interaction
between tip and surface
• Tip broadening: radius of curvature of the tip > size of the feature to be imaged
• Artefacts/Hysteresis effects or cross-talk influences the image

6.7 AFM vs SEM Comparison

Feature AFM SEM

Image Type True 3D surface profile 2D projection / image
Sample Preparation No special treatment needed Requires metal/carbon coating for
non-conductors
Environment Works in air or liquid Requires expensive vacuum
Resolution True atomic resolution (UHV) ~10 nm typically
Sample Conductivity Not required Required (or coating needed)
Scan Area ~150 × 150 micrometers max Millimeters by millimeters
Biological Samples Suitable, even living organisms Limited — vacuum & coating
issues