Analytical Methods

MSE528
Chemical analysis
Structural Analysis
Physical Properties
X-Ray method
Laue Techniques: rotating Xtal
Debye-Scherrer: Powder Method
Diffraction
Electron Microscope
Transmission Electron Microscope (TEM)
Scanning Electron Microscope (SEM)
SPM & AFM

Microanalysis: EDAX, AES and XPS


X-Ray method
Laue Techniques: rotating Xtal
Debye-Scherrer: Powder Method
Diffraction

X-ray powder diffraction (XRD) is one of the
most powerful technique for qualitative and
quantitative analysis of crystalline
compounds. The technique provides
information that cannot be obtained any
other way. The information obtained includes
types and nature of crystalline phases
present, structural make-up of phases,
degree of crystallinity, amount of amorphous
content, microstrain & size and orientation of
crystallites.
X-ray diffraction has application in most fields dealing with solid
materials. XRD identifies crystalline compounds as opposed to X-ray
Fluorescence (XRF) or other spectro-chemical methods that identifies
just the elements. Areas of application are quite wide and include
metals, organic and inorganic compounds.

Some of the relevant areas are listed and discussed below:
Airborne dusts and particulate
Hazardous Inorganic chemicals
Asbestos
Metals
Biomaterials
Pharmaceuticals
Catalysts
Polymers
Ceramics and Composites
Rocks and minerals
Clays & Soils
Semiconductors
Corrosion Products

A schematic of typical optics is shown below.

Typically for a fine filament tube the filament length Lx is 12-16mm and its width Wx is 0.04mm.

nl = 2d sin q
In the scanning electron microscope (SEM) a very fine 'probe' of
electrons with energies up to 40 keV is focused at the surface of the
specimen in the microscope and scanned across it in a 'raster' or pattern
of parallel lines. A number of phenomena occur at the surface under
electron impact: most important for scanning microscopy are the
emission of secondary electrons with energies of a few tens eV and re-
emission or reflection of the high-energy backscattered electrons from
the primary beam. The intensity of emission of both secondary and
backscattered electrons is very sensitive to the angle at which the
electron beam strikes the surface, i.e. to topographical features on the
specimen. The emitted electron current is collected and amplified;
variations in the resulting signal strength as electron probe is scanned
across the specimen are used to vary the brightness of the trace of a
cathode ray tube being scanned in synchronism with the probe. There is
thus a direct positional correspondence between the electron beam
scanning across the specimen and the fluorescent image on the cathode
ray tube.

The magnification produced by scanning microscope is the ratio between
the dimensions of the final image display and the field scanned on the
specimen. Usually magnification range of SEM is between 10 to 200 000
X. and the resolution (resolving power) is between 4 to 10 nm (40 - 100
Angstroms) .


How the SEM Works

The SEM uses electrons instead
of light to form an image. A
beam of electrons is produced
at the top of the microscope by
heating of a metallic filament.
The electron beam follows a
vertical path through the column
of the microscope. It makes its
way through electromagnetic
lenses which focus and direct
the beam down towards the
sample. Once it hits the sample,
other electrons ( backscattered
or secondary ) are ejected from
the sample. Detectors collect the
secondary or backscattered
electrons, and convert them to a
signal that is sent to a viewing
screen similiar to the one in an
ordinary television, producing
an image.

JEOL JSM-7500
Mag: 25 to 1,000kX
kV: 0.1 to 30kV
SEI: 1.0nm (15kV)
SEI: 1.5nm (1kV)
SEI: 4.0nm (0.1kV)
BEI*: 1.5nm (5kV)
BEI*: 1.7nm (3kV)
GB mode / r-filter / in-
lens BSE Detector

Highlights of the 7500F
5 axis tilt eucentric stage with automation standard on
all axes including compeucentric rotation.
Smooth mechanical stage movement at high mags via
TEM trackball & touch pad
Great low kV SE, low kV BSE and STEM Imaging
Enhanced environmental resistance
GB Mode and in column SE energy filter
In lens BSE Detector for ultra high res. BSE imaging
LABE detector
r-Filter

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Live Image Comparison
The main image window can also be a live split or live quad display of
different detector signals with independent control of each signal
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Specimen
stub Specimen
Electron probe
Electron
Electron probe


Gentle Beam
Reduces the effect of charging
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Gentle Beam
Increases resolution by maintaining higher kV in the
gun & column. (Reduces Aberrations)
Accelerates secondary electrons off the sample,
especially at very low accelerating voltages.
Reduces charging.
Reduces contamination.
Lowers the kV to the sample increasing pure surface
topographic detail due to reduced beam penetration.
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Gentle Beam
1KV X100,000 1KV X100,000
SEM Mode Resist Lines & Spaces Gentle Beam Mode
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0.1kV in GB mode
50,000X 200,000X
Mesoporous Silica
Ultra-High Resolution SEM JSM-7500F
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STEM Data
C Nano Tubes
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EDS Spot Analysis in STEM
Sample: Carbon nanotube with catalyst particles
Mag: x 220,000
Acc. Voltage: 30kV
Imaging mode: STEM

EDS spot analysis clearly distinguishes between
Fe-containing catalyst particles (Spot A) and
carbon nanotube matrix (Spot B)
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Electron Spectroscopy for Chemical Analysis (ESCA) or
X-ray Photoelectron Spectroscopy (XPS)

In a failure analysis technique primarily used in the identification of compounds on
the surface of a sample. It utilizes X-Rays with low energy (typically 1-2 keV) to
knock off photoelectrons from atoms of the sample through the photoelectric
effect. The energy content of these ejected electrons are then analyzed by a
spectrometer to identify the elements where they came from.

The incident X-Rays used in knocking off the electrons must possess energy that is
both monochromatic and of accurately known magnitude. The X-ray source
material must also be a light element since X-ray line widths, which must be as
narrow as possible in ESCA, are proportional to the atomic number of the source
material. It is for these reasons that commercial XPS systems typically use the K-
alpha X-rays of aluminum (Al K-alpha E = 1.487 keV) and magnesium (Mg K-alpha
E = 1.254 keV).

Schematic representation of the energies produced
from electron beam interaction with solid matter.
Luminescence is the emission of light from a solid
which is 'excited' by some form of energy. The term
broadly includes the commonly-used categories of
fluorescence and phosphorescence.
Field Emission Scanning Electron Microscopy (FESEM) is a
high-resolution imaging technique providing topographical and
structural information in plan view or in cross-section. Often
used in conjunction with SEM, Energy Dispersive X-Ray
Spectroscopy (EDX) is used to qualitatively and quantitatively
analyze the elements present in a selected area of the SEM
image. Together FE-SEM and EDX capabilities allow the
irradiation by a focused electron beam, imaging secondary or
backscattered electrons and energy analysis of x-rays.
Typical SEM applications include plan view and cross-sectional
imaging for process development and failure analysis. EDX
applications include specific defect analysis or compositional
analysis (for boron and heavier elements).

2.1nm resolution at 1kV
1.5nm resolution at 15kV
Cold finger and specimen exchange chamber
as standard
Optional integrated EDX system with 30
degree take-off angle
Fully digital imaging, image processing and
archiving system
Dual SE detectors for versatile imaging
New ExB energy filter

Compositional analysis
Elemental
Chemical
Electron diffraction/crystalographic
identification
Phase identification


Silicon devices
Precise Location
Compound semiconductors
Magnetic disks
Film Thickness
Gate Ox thickness
III - IV Superlattice
Step coverage
Gate Ox thickness
Gate to Silicon Interface
Interfacial oxide




Chemical analysis (microanalysis) in the scanning
electron microscope (SEM) is performed by measuring
the energy or wavelength and intensity distribution of X-
ray signal generated by a focused electron beam on the
specimen. With the attachment of the energy dispersive
spectrometer (EDS) or wavelength dispersive
spectrometers (WDS), the precise elemental
composition of materials can be obtained with high
spatial resolution. When we work with bulk specimens in
the SEM very precise accurate chemical analyses
(relative error 1-2%) can be obtained from larger areas
of the solid (0.5-3 micrometer diameter) using a n EDS
or WDS. Bellow is a example of EDS spectrum collected
in the SEM with EDS. The spectrum shows presence of
Al, Si, Ca, Mn and Fe in the steel slag phase.
Scanning Acoustic Microscopy (SAM) is an excellent technique for studying
buried solid interfaces of dissimilar materials. SAM is an internal imaging
analysis technique produced via ultrasonic waves reflecting or transmitting
at sample interfaces. The images are constructed by detecting reflection
(echo) or transmission of ultrasound from a solid state device shortly after
pulse-excitation by a focusing transducer. Features such as bonded
interfaces, density gradients or defects (delaminated interfaces, voids and
cracks) can be imaged non-destructively.
FTIR application
What is FTIR?
Applications of FTIR (general)
Applications of FTIR for semiconductor
industry
Remarks
FTIR
Fourier Transform Infrared Spectroscopy
Used for identifying or characterizing
organic (and some inorganic) compounds
(solid, powders, residues, solvents, liquids,
gas)
IR radiation is absorbed/transmitted;
resulting spectrum characteristic of
molecular structure
FTIR
Fingerprint type method (no 2 are same)
Detection of individual chemical compounds
or characteristic absorptions of chemical
functional groups (organic and some
inorganic)
Detection limit: picogram range
(monomolecular layers detectable on metal
surfaces)
Qualitative, quantitative
Reference libraries, spectral interpretation
Sampling techniques: transmission,
external reflection, internal reflection (ATR),
diffuse reflection, emission, and
photoacoustic spectroscopy
Detectors: triglycine sulfate (TGS), mercury-
cadmium-telluride (MCT)

FTIR with microscope
General Applications
Identify unknown compounds
-e.g. plastics, drugs (i.e. cocaine),
contamination (i.e. flux residues,
silicone, esters, grease, etc.)
Obtain structural information (organic functional groups)
-e.g. alkanes, alkenes, alkynes, aromatics, alcohols,
ethers, amines, aldehydes and ketones,
carboxylic acids, amides, etc.
Common uses in semiconductor
industry
Determination of interstitial oxygen and substitutional carbon
in processing wafers
Epitaxial film thickness measurements
Monitoring phosphorus in phosphosilicate thin films and both
phosphorus and boron in borophosphosilicate thin films
Measurement of the hydrogen content in oxide and nitride thin
films
Identification of particles and residues (most common)
Incoming materials characterization
Trace gas analysis
Carrier concentration measurements
Characterization of Si surfaces after cleaning operations
Measurement of Interstitial Oxygen
and Substitutional Carbon in Si
Wafers
Si-C, Si-O-Si
Advantages of FTIR for measurement of Cs
and Oi
Non-destructive
Cheaper
Faster
Reproducible
Sensitive (to dopants)
Excellent spatial resolution (5-10 um)
Specific to the Oi and Cs in Si
Epitaxial Film Thickness Applications
To determine epitaxial (Epi) layer film thickness
(the most commonly used high-resistivity Epi
layers are transparent to IR radiation)
3 methods (constant-angle observations making
use of either direct or modified measurement of
interference phenomena):
1) Interferogram Subtraction
2) Constant Angle Reflection Interference Spectroscopy
3) Cepstrum
Interferogram Subtraction
Constant Angle Reflectance
Interference
Advantages of FTIR for Epi thickness
measurements
speed of measurement
Non-destructive
Reproducible
Lends itself to automation
Operator independent
Particle/residue identification in Failure Analysis
Remarks
Many applications
May use other instruments/tools/techniques to
obtain additional information or confirmation
Relatively cheap, quick, accurate, internally
calibrated (self-calibrated)
Even with software and automation, still
recommend a chemist familiar with spectral
interpretation