Ftir

FTIR Seminar
Chapter 1 Principles and Fundamentals of Infrared Spectroscopy

Chapter 2 Principles of FTIR
Chapter 3 Standard Data Processing Features
Chapter 4 Transmittance Techniques
Chapter 5 Reflectance Techniques
Chapter 6 Quantitative Analysis (Optional Software)
Chapter 7 Infrared Spectrum Analysis Techniques
JASCO FTIR Seminar Chapter 1
Principles and Fundamentals of Infrared Spectroscopy
FTIR Seminar
Chapter 1
Principles and Fundamentals

of Infrared Spectroscopy
Chapter 1-1 FTIR seminar
Infrared absorption Principles
spectrum and Fundamentals of Infrared Spectroscopy
Infrared absorption spectrum
100
80
60
%T
40
20
0
4000 2000 1000 400
Wavenumber [cm-1]
Principles
Types of Electromagnetic Radiationand Fundamentals of Infrared Spectroscopy
Types of Electromagnetic Radiation
1m Radio waves
Microwaves
1mm=1000µm 10cm-1
Far infrared
25µm 400cm-1
Infrared
2.5µm 4000cm-1
Near infrared
0.7m=700nm 14000cm-1
Visible light
400nm
Near UV
2000A Ultraviolet
Far-UV
500A
X-rays
0.05A=50XU
Gamma rays
1XU
Cosmic rays
Interaction betweenPrinciples and Fundamentals
Molecular Dynamics and Light of Infrared Spectroscopy
Interaction between Molecular Dynamics and Light
Molecular energy = electronic energy Molecular energy level

+ vibrational energy
+ rotational energy
Excited
state
Light Emission of energy

E as heat
absorption
Ground
state
E
Electronic energy .=. Visible light and ultraviolet energy

Vibrational energy .=. Infrared energy
.
Rotational energy =. Near-infrared energy
Molecular Vibration Principles and Fundamentals
of Diatomic Molecules of Infrared Spectroscopy
Molecular Vibration of Diatomic Molecules

Infrared light and a molecule only interact when the dipole moment of the molecule
changes due to vibration
Spring between two spheres
Heteronuclear diatomic molecules : HCI, CO Infrared active
Homonuclear diatomic molecules : O2, H2, N2, and CL2 Infrared inactive
Principles
Vibrational Frequency and Fundamentals
of Diatomic Molecules of Infrared Spectroscopy
Vibrational Frequency of Diatomic Molecules

The Vibrational Frequency of a diatomic molecule for which the absorption position,
bond strength = spring strength, can be expressed by the following equation
f : strength constant (bond constant and bond order)

m and m’ : mass number of atom
C : Speed of light
Chapter 1-6-1 FTIR seminar
Principles
Normal Frequency of and Fundamentals
Triatomic Molecules (CO2) of Infrared Spectroscopy
Normal Frequency of Triatomic Molecules (CO2)
CO2: linear molecule

(1) Symmetric stretching vibration
O C O Infrared inactive
(2) Asymmetric stretching vibration
O C O 2349cm-1
(3) Deformation vibration
O C O
667cm-1 Degeneracy
O C O
Chapter 1-6-2 FTIR seminar
Principles
Normal Frequency of and Fundamentals
Triatomic Molecules (H2O) of Infrared Spectroscopy
Normal Frequency of Triatomic Molecules (H2O)
(1) Symmetric stretching vibration H2O : nonlinear molecule
O
3652cm-1
H H
(2) Asymmetric stretching vibration

O
H H 3756cm-1
(3) Deformation vibration
O
H H 1595cm-1
Principles
Number of Normal Frequencies and Fundamentals of Infrared Spectroscopy
Number of Normal Frequencies
The number of normal frequencies of a molecule consisting of n atoms can be determined by

the following calculations:
Linear molecule 3n-5

Nonlinear molecule 3n-6
Example :
3x3-5=4
3x3-6=3
Molecular Vibration Principles and Fundamentals
of Polyatomic Molecules of Infrared Spectroscopy
Molecular Vibration of Polyatomic Molecules
Example : Acetaldehyde
Absorption Position Principles and Fundamentals of Infrared Spectroscopy
Absorption Position
Gamma rays X-rays Ultraviolet Visible light Infrared Microwaves
(C=C, C=N)
O-H, N-H
(C=O)
-H
C-H
(C-C, C-O, C-N)
Etc.
4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400
Wavenumber (cm-1)
Principles
An Example of Assignment and Fundamentals of Infrared Spectroscopy
An Example of Assignment
Polyethylene
100
80
60
%T Methylene rolling vibration
40
20 Methylene scissoring vibration

C-H stretching vibration
04000 2000 1000 400
Wavenumber[cm-1]
Polystyrene
100
80
Harmonics and
60 combination
tones of an out-
%T C-H
40 stretching of-plane
deformation Skeletal
vibration of a
vibration vibration of
20 benzene ring
benzene
rings
0 4000 2000 1000 C-H out-of-plane 400
Wavenumber[cm-1] deformation vibration
Absorption StrengthPrinciples and Fundamentals of Infrared Spectroscopy
Absorption Strength
Absorption strength depends on the size of deformation of the dipole moment due to vibration
Deformation of the dipole moment is large : strong absorption C=O, C-X

Deformation of the dipole moment is small: weak absorption C-C
Principles
Near-Infrared Absorption and
Spectrum Fundamentals of Infrared Spectroscopy
Near-Infrared Absorption Spectrum
Principles of absorption
Harmonics or combination tones of normal frequencies
Primarily O-H, N-H, and C-H
Weak absorption compared to the infrared region
Spectrum shape is complex
Analysis
A recent trend is quantitative analysis by the application of Chemometrics
Main Applications
Nondestructive analysis in agriculture- and food-related fields
Principles
Far-Infrared Spectrum and Fundamentals of Infrared Spectroscopy
Far-Infrared Spectrum
Absorption principles
Vibrations of heavy atoms and weak bonds

Example : Metals such as copper and tin
Sulfur and iodide
Coordinate bonds (complexes)
Rotation
Principles
Conclusion of Chapter 1 and Fundamentals of Infrared Spectroscopy
Conclusion of Chapter 1
(1) Region
Infrared : 4,000 to 400 cm-1

Produces information on molecular vibration and rotation
Near infrared : above 4,000 cm-1

Almost entirely harmonic peaks of normal frequency
Samples containing moisture can also be measured
Introduced in the fields of processed foods and agriculture
Far-infrared : below 400 cm-1

Molecular rotation information
Metal oxides, metal compounds, and organic and inorganic metal complexes
Principles
Conclusion of Chapter 1 and Fundamentals of Infrared Spectroscopy
Conclusion of Chapter 2
(2) Analysis targets : Organic and inorganic substances
(3) State : Gas, liquid, and solid
(4) Analysis description

Qualitative analysis
Functional group analysis
Determines the existence of functional groups by
the presence of specific functional group peaks.
Pattern analysis
Estimates compound materials by comparing standard spectra
Quantitative analysis
The strength (absorbance) of the absorption band
is proportional to the amount of the material.
Quantitative analysis is possible.

Principles of FTIR
FTIR Seminar
Chapter 2
Principles of FTIR
Principles
Process up to Obtaining of
a Spectrum FTIR
Process up to Obtaining a Spectrum
Sample (S)
Measurement : Interferogram
Fourier transform process
SB
Transmission spectrum
Interferometer
4000 400
Wavenumber[cm-1]
(S) / (B) %T
Light
source
Background (B)
4000 400
Wavenumber[cm-1]
SB
4000 400
Wavenumber[cm-1]
Spectroscope Principles of FTIR
Spectroscope
Computer
Light
source
Sample Electrical system

Interferometer Detector
chamber circuits
Infrared Interference Absorption Optical Signal sampling

light waves signal Fourier transform
Analog signal
(Interferogram)
Electrical Digital signal IR spectrum

signal
IR light source Principles of FTIR
IR light source
Intensity Distribution and Temperature Dependency versus Wavelength of

Black Body Radiation Energy
105
6000K
104
4000K
103
Spectral irradiance W λ
102 2000K
10
1000K
1
10-1
500K
10-2
300K
10-3
200K
10-4
0.1 0.2 0.5 1 2 5 10 20 50 100
Wavelength λ / µm
FT Optical SystemPrinciples
Diagram of FTIR
FT Optical System Diagram
Light He-Ne gas laser

source
(ceramic)
Beam splitter
Movable mirror
Sample chamber
Fixed mirror
Detector
Interferometer
(DLATGS)
Principles
Interference of Two of
Beams of Light FTIR
Interference of Two Beams of Light
Movable mirror
Fixed mirror
Ａ
Movable mirror
Same-phase interference
wave shape
-2λ -λ 0 λ 2λ
Fixed mirror
Continuous phase shift
Ｂ
Signal strength
Movable mirror Ｉ
Opposite-phase (X)
interference
wave shape
Fixed mirror
Ｃ
Movable mirror
-2λ -λ 0 λ 2λ
Same-phase interference
0 λ wave shape Ｄ Interference pattern of light
manifested by the optical-path
difference
Principles of
Interference Is a Superpositioning of FTIR
Waves
Interference Is a Superpositioning of Waves
Relationship between light source spectrum and the signal output from interferometer
Light source spectrum I Signal output from interference wave
(a) Monochromatic light

Az
Wavenumber υ
Time t
Σ I
(b) Dichroic light

ΣAz
Wavenumber υ Time t
I(t)
(c) Continuous spectrum light
β (υ)
Wavenumber υ Time t
● All intensities are standardized.
Principles
Sampling of an Actual of
Interferogram FTIR
Sampling of an Actual Interferogram
Interferometer interferogram
Output of a Laser interferometer
Primary interferometer interferogram that was sampled
Optical path difference x

Fourier transform Principles of FTIR
Fourier transform
Single strength
Fourier transform SB
Optical path difference[x] 4000 Wavenumber[cm-1] 400
(Interferogram) (Single beam spectrum)
Time axis by FFT Wavenumber

Detector PropertiesPrinciples of FTIR
Detector Properties
MCT
Operates at the temperatur
1010 of liquid nitrogen
D* (λ, f) (cmHz1/2W-1)
109
TGS
Operates at room temperature
108
4000 600
Wavenumber[cm-1]
Principles
Measurement Parameters of FTIR
Measurement Parameters
Resolution : Fixed, qualitative analysis of liquid sample: Standard 4 cm-1

Gas analysis, peak shift study, and band resolution etc: High resolution
The larger the maximum optical path difference of the interferometer, the
higher the resolution
Number of integrations : Approx. ten times normal gain

The goal is to improve the SN ratio. SN ratio improvement can be expected at
multiples of the integration count root
Apodization function : Standard Cosine

Since the movable mirror can only move a certain distance,
discontinuity arises in the data. Apodization is an operation that
treats the end of the interferogram so that there is no difference in level.
Apodization is concerned with the shape of peaks
(including their sharpness and half-value width)
Zero filling : Interpolation of data (smoothes out data)

Standard Data Processing Features
FTIR Seminar
Chapter 3
Standard
Standard Data Processing Data
Features Processing Features
Baseline correction : Fixes curved baselines

Extraneous peak elimination : Cuts absorption peaks for atmospheric carbon dioxide gas (CO2)
Smoothing : Reduces noise by means of computer processing
Difference spectra : Decomposition of spectra containing multiple components etc.
Peak processing : Computation of peak position, height, area, and half-value width
Ordinate axis conversion : %T <-> Abs etc.
KM conversion : In the diffuse reflectance method, conversion of transmissivity
to the y axis proportional to temperature
KK conversion : Conversion of an abnormal spectrum affected by the sample’s
refractivity to an absorption spectrum
ATR correction : Use of ATR to correct spectrum distortion
Mathematical operations : Mathematical operations for two spectra or a spectrum and constant
Differential : Differential of spectra
Others
Deconvolution: Extraction of peak positions in each band
FFT filtering: Eliminates from spectra only noise possessing a specific cycle
Data cutting: Cuts measured spectra to any wavenumber region
Curve fitting: Band decomposition
Validation: Instrument performance check
Baseline CorrectionStandard Data Processing Features
Baseline Correction
Relationship of particle size

Property of light: Light scatters when it strikes a particle larger than its own wavelength
100
Scattered light
Infrared light Particle %T
Scattered light 0
4000 Wavenumber[cm-1] 400
Effect of sample refractivity

A sample containing carbon has high Among the effects of this refractivity is a lower
refractivity base to the right
100
%T
40
Correction ExampleStandard Data Processing Features
Correction Example
Baseline Correction
After-correction
100 100
%T 50 %T 50
0 0
4000 Wavenumber[cm-1] 400 4000 Wavenumber[cm-1] 400
CO2 Elimination Standard Data Processing Features
CO2 Elimination
When a large CO2 peak appears in a spectrum,
mathematical processing is used to eliminate it.
CO2 absorption peaks appear near 2,350 and 670 cm-1.
Before-elimination 100
After-elimination
100
%T %T
CO2
30 30
Wavenumber[cm-1] 4000 Wavenumber[cm-1] 650
4000 650
Difference Spectra Standard Data Processing Features
Difference Spectra
(Target component + known component) - known component = target component
1.0
Temperature correction
Abs Abs
0.0 -0.1
4000 Wavenumber[cm-1] 650 4000 Wavenumber[cm-1] 650
1.0
Blue line: adhesive Adhesive - hot-melt nylon

Red line: hot-melt nylon = acrylic polymer
Transmission Techniques
FTIR Seminar
Chapter 4
Transmission
Types of Transmission Techniques Techniques
Types of Transmission Technique
Primarily qualitative analysis of organic

KBr disk or inorganic substances in powder form
technique or that can be made into powder form
Polymeric qualitative and quantitative

Solid samples Thin-film
technique
analysis for substances in film form
or that can be made into film form
Primarily qualitative analysis of

Solution
substances dissolved in solvent
technique
(uses liquid cells)
Primarily qualitative analysis of

Liquid film viscous and nonvolatile substances
technique
(sandwiched between KBr windows)
Liquid samples
Primarily qualitative analysis of liquids
Solution
that dissolve in solvent and nonvolatile
technique
substances (uses liquid cells)
Transmission
KBr Pellet Technique Techniques
KBr Pellet Technique
Disk press Microdisk press

Disk diameter 10 mm φ 5 mm 3 mm 2 mm
Sample amount 500 µg 100 µg Several 10's Several µg

of µg
KBr amount 150 mg 20 mg 10 to 7 mg 5 to 3 mg
Pressure 7t 1t Hand press Hand press
What You Need

3mmφ Protuberance
- KBr crystals (for IR) is different!
- Microdisk press
- Hand press
- Disk holder
Transmission
How to make disks Techniques
How to make disks
Short
protuberance
Insert powder
Apply pressure with

Place in holder hand press
and measure
Thin-film Technique
Thin-film Technique
Spread out thinly

using a spatula or
similar implement
Sample
Window
Add drops of solvent Measure once the

to dissolve sample solvent evaporates
Transmission
Liquid-film Technique Techniques
Liquid-film Technique
Screw
Sandwich the sample between two windows Windows
Rubber backing
Sample
Cell frame
Assembly cell
Place and measure the assembly cell
What You Need Spacer (Al or Pb)

- Windows
- Assembly cell Sample
- (Spacer) Spacer Windows
- Silicone cloth Rubber Cell frame
backing
Transmission
Solution Technique Techniques
Solution Technique
Dissolve the sample in an appropriate

infrared solvent, place it in a fixed
liquid cell , and then measure.
Stopper
Sample inlet
What You Need Stopper
- Fixed cell for liquid
- Solvent Metal frames
Chloroform
Carbon tetrachloride Sample outlet
Carbon dioxide
Spacer
Window
How to DetermineTransmission
Cell Thickness Techniques
How to Determine Cell Thickness
Measure the empty cell to find the interference curve.

Transmission
Materials That Transmit Infrared Techniques
Materials That Transmit Infrared (1)
Materials That Transmit Infrared
Refractivity Melting Point Applicable Water-Solubility

Material (Approx.) Range(cm-1)
Notes
(oC) (g/100g Water)
No mechanical strength
KBr 1.5 730 43500 to 400 53.5
Easily broken
Dissolved in an ammonia
CaF2 1.4 1360 77000 to 1100 0.0017 salt solution
Affected by acidic solutions

KRS-5 2.4 414 20000 to 250 0.05
Soft and easily damaged
10000 to 500 Dissolves in HNO3

ZnSe 2.4 1100 (For ATR: Insoluble
up to about 650) Easily broken
5500 to 500 Dissolves in warm sulfuric acid

Ge 4.0 936 (For ATR: Insoluble
up to about 700) Easily broken
Transmission
Materials That Transmit Infrared Techniques
Materials That Transmit Infrared (2)
Materials That Transmit Infrared

CaF2 KBr KRS-5
100
ZnSe
%T 50
Ge
-10
6000 4000 2000 400
Wavenumber[cm-1]
JASCO FTIR
JASCO Seminar
FTIR Chapter
Seminar 45
Chapter
Reflection Techniques
FTIR Seminar
Chapter 5
Reflection Techniques
Reflection
Types of Reflection Techniques Techniques
Types of Reflection Technique
Elastic and viscous substances that are

ATR technique insoluble, infusible, and difficult to grind
up Information of sample surface
Diffuse Substances in powder form or that

Solid samples reflectance can be turned into powder
technique Those with surfaces that are rough.
Specular Film on a metal substrate

reflection (around 0.1 to 5 µm)
technique Solids with a smooth surface
Thin film on a metal substrate

RAS technique (around 10 angstrom to 1 µm)
ATR technique Measurement of aqueous solutions
Liquid samples
Diffuse Measurement of aqueous solutions
reflectance (eliminate water)
technique
ATR Technique Reflection Techniques
ATR Technique
Incident Reflected
light light
Prism
Sample
Reflection
Depth of Light Penetration Techniques
into Sample
Depth of Light Penetration into Sample
Depth of Light Penetration into Sample

Depth of light penetration into sample is determined by:
1. Wavelength (µm)
2. Incident angle (η)
3. Refractivity of prism (n1) and sample (n2)
Proportional to wavelength
λ
dp = [sin2θ - (n2/n1)]-1/2
2πn1
dp : depth of penetration
Inversely proportional to prism refractivity

Reflection
Types of ATR Prisms Techniques
Types of ATR Prisms
Measurable n2
Wavelength n1 Measurement Target
θ =45 θ =60
o o
Range
KRS-5 up to 250 2.4 1.7 2.1 General organic materials
General organic materials

ZnSe up to 625 2.4 1.7 2.1 and aqueous solutions
Ge up to 700 4.0 2.8 3.5 Rubber containing carbon

and extremely thin surfaces
θ : incident angle n2
n1 : prism refractivity >
sin θ = n1
n2 : sample refractivity
(upper limit of sample refractivity for producing total reflection)
Reflection
Relationship between wavelengthTechniques
and incident angle
Relationship between Wavelength and Incident Angle
Relationship between Wavelength and Incident Angle to depth of

penetration by prism type
Wavelength (µm)
0 2 4 6 8 10 12 14 16 18 20
Prism Refractivity
2.5
KRS-5 n1=2.4
ZnSe
2.0
Dp (µm)
1.5
Ge n1=4.0
1.0 Sample refractivity n2 = 1.5

Incident angle θ = 45o
0.5
833
714
625
555
500
5000
2500
1666
1250
1000
Wavenumber (cm-1)
Reflection
Measurement of Rubber Techniques
Containing a High Concentration of Carbon
Measurement of Rubber
Containing a High Concentration of Carbon
Attachment: ATR-300/H
Prism: Ge
Integrations: 20
Resolution: 4 cm-1
Detector: TGS
Normally, the ATR technique is
employed to measure rubber Before-baseline correction
The material for the prism is selected

based on the amount of carbon
contained in the rubber
A Ge prism is used when the carbon
content is high, and when the baseline is %T
curved it is corrected
After-baseline correction

ATR Correction Reflection Techniques
ATR Correction
2.2
Before-correction
After-correction
Abs
-0.1
Attachment: ATR-500/M
Integrations: 30
Resolution: 4 cm-1
Reflection
ATR Technique Features Techniques
ATR Technique Features
Surface layer information can be measured in a nondestructive manner
No need for sample preparation, and state analysis is possible
By selecting the correct prism, it is possible to adjust the depth of light

penetration into the sample
Using a holder for liquid allows measurement of aqueous solutions as

well
Reflection
Cautions on Usage Techniques
Cautions on Usage
In most cases, the reason for failing to obtain a good spectrum is a poor bond between
the sample and prism. Care must be taken with samples lacking a smooth surface and
those that are hard because a layer of air can easily form between the sample and the
prism during bonding.
Since ZnSe and Ge crystals are fragile, be careful not to apply too much pressure to them
or strike or drop them.
Since ZnSe and Ge have absorption in the low wavenumber region, verify the measurable
range.
If a ZnSe prism fails to yield a good spectrum when measuring a material such as rubber
containing carbon, use a Ge prism instead.
How to clean a prism:

KRS-5 : Rinse the prism with chloroform or similar fluid, being careful not to touch it.
ZnSe and Ge :Dampen a Kimwipe or similar wipe product with solvent and lightly wipe
the prism.
The KRS-5 should be stored in a desiccator

Applications Reflection Techniques
Applications
The ATR technique can be applied to measure

the following types of substances:
Elastic and viscous substances that are insoluble, infusible, and difficult to grind up
Rubber, urethane foam, synthetic leather, and thermoset resin
Substances difficult to measure using the thin-film technique

Polymeric thin films
Surfaces consisting of an extremely thin layer that is difficult to measure

Measurement of coatings such as paint, varnish, and lacquer and their change over time
Measurement of adhesive tape and electrical tape surfaces
Identification of coating materials such as paper, metal, cloth, and leather
Measurement of aqueous solutions

Reflection
Diagram of Diffuse Techniques
Reflectance Principle
Diagram of Diffuse Reflectance Principle
Diffusely reflected light R1

Incident angle I０
Reflected light R0
Reflection
Kubelka-Munk Equation Techniques
Kubelka-Munk Equation
Kubelka-Munk Reflection Techniques
Kubelka-Munk
5
ABS
4 K/M
Qualitative analysis: ABS: 2 or less

3
K/M: 10 or less
Intensity
2 Quantitative analysis: ABS: 1 or less
K/M 3 or less
1
0 10 20 30 40 50 60 70 80 90 100
Reflectivity
Reflection
Spectra of Trehalose Techniques
Spectra of Trehalose
DR method after dilution
100
80
KBr pellet method

60
%R DR method without dilution

40
20
0
4000 2000 1000 400
Wavenumber[cm-1]
Reflection
Spectra of Trehalose Techniques
Spectra of Trehalose
0.4
0.3 After dilution
K/M 0.2
Without dilution
0.1
0
4000 2000 1000 400
Wavenumber[cm-1]
Features Reflection Techniques
Features
(1) Can be used on powder samples and samples with rough

surfaces
(2) Obtains a spectrum resembling a transmission spectrum but

with a slight difference in the intensity ratio
=> Weak absorption in the transmission spectrum is enhanced by
the DR spectrum
(3) Compared to the KBr technique, the sampling operation is

easier
(4) Quantitative analysis is also possible by switching to the K/M

function (only when the K/M value is 3 or less)
(5) In addition to room temperature, measurement during or after

heating is possible. Attachments are available for that purpose
Reflection
Important Information ConcerningTechniques
the Diffuse Reflectance Technique
Important Information
Concerning the Diffuse Reflectance Technique
(1) Samples should be in the finest powder form possible

(a particle size of 20 µm or less is best)
Prevents specular reflection
Increases number of reflections, thereby
enhancing absorption
(2) Dilute samples with KBr

Dramatically lowers specular reflection
Enables the dilution ratio to be obtain
corresponding to the measurement target
(normally, around several percent)
(3) When focusing on OH groups, use CaF2 powder

instead of the highly hygroscopic KBr powder
Applications
Substances that can be measured using the normal KBr technique
Substances difficult to measure using the KBr technique (includes

clay, cement, minerals, and pigment)
Research on adsorption/desorption reactions on catalyst surfaces

Reflection
Principles of the Specular Techniques
Reflection Technique
Principles of the Specular Reflection Technique
I I0 I I0 I1 I2
θ θ
n1 Medium (air) n1
n2 Thin film n2 d
Metal n3
Reflection
Kramers-Kronig Transform Techniques
Kramers-Kronig Transform
7.0
By transforming the surface of a Pre-conversion
resin or plastic into a specular
surface, it is possible to capture faint %T
reflected light and obtain the
reflection spectrum.
2.0
The reflection spectrum is affected 4000 Wavenumber[cm-1] 400
by the sample’s refractivity (n), K/K Transform

causing its waveform to change.
0.2
This example if for software that Post-conversion
converts the reflection spectrum into

k
an absorption spectrum.
0.0
Reflection
Kramers-Kronig Transform Techniques
Kramers-Kronig Transform
KK Transform
1.6
1
Reflection
Spectrum
-0.8
4000 2000 1000 400
Wavenumber[cm-1]
Features
(1) Can obtain spectra simply by placing a sample with a smooth

surface. However, the K/K transform is required to contrast with the
normal transmission spectrum.
(2) Enables state analysis of thin film (approximately 5 µm or less) on

a metal substrate.
Reflection
Specular reflectance method Techniques
Specular reflectance method
1.6
1.5
Cut off sample

and KBr method
1
Specular
reflectanc
Abs e method
0.5
0
4000 2000 1000 400
Wavenumber[cm-1]
Reflection
Cautions on Usage
(1) The measurement surface must be either a specular surface or smooth

surface.
(2) The reference sample should be a substance as close as possible to the

sample. When a reference is not available, a mirror can be used instead.
(3) When measuring coating film on a reflective substrate, the film thickness
should be between 0.1 and 5 µm.
Applications
(1) Analysis of film coatings on metal surfaces, deposits, and oxide films
(2) Analysis of samples that have a smooth surface and are difficult to
measure using the transmission technique
(3) Measurement of epitaxial layer thickness
(4) Measurement of relative reflectivity

Applications
0.23
0.2
Transmittance
spectrum
Abs
0.1
Reflectance
spectrum
0
4000 2000 1000 400
Wavenumber[cm-1]
Reflection
High-Sensitivity Reflection Techniques
Technique
High-Sensitivity Reflection Technique
Reflection of linearly polarized light on a metallic surface: In the case of p polarization
Standing waves
Electric vector of Electric vector of

reflected light incident light
Features
(1) Enables the qualitative and quantitative analysis of thin film of around
several tens of Å to several µm that has been processed on the surface of a
metal substrate.
(2) Absorption increases as the dipole moment approaches 90 degrees.
(3) Most sensitive method for measuring thin-films on the surface of metal
substrates.
Reflection
Cautions on Usage
(1) The transmission spectra and patterns of RAS spectra differ depending on the surface
selection ratio.
(2) This technique should be applied to thin films on the surface of smooth metal substrates.
(3) Notes on handing samples:

Handle samples with tweezers (avoid putting fingerprints on samples).
Do not expose the samples to the open air except when measuring
(avoid contamination by airborne debris).
(4) Make sure no absorption exists that will interfere with the reference (unprocessed metal
substrate).
Applications
(1) Analysis of surface processing and adsorption of metal substrates and

semiconductor substrates
(2) Residue check after washing metal substrates and semiconductor substrates
(3) Measurement of LB films
(4) Qualitative analysis of compact disc surface lubricating oil

Applications
0.40
0.30
RAS
0.20
Abs
0.10
RF
0.00
-0.05
4000 2000 1000 400
Wavenumber[cm-1]
Applications
RF
Abs=0.001
Abs
RAS
Abs=0.31
4000 2000 1000 400

Wavenumber[cm-1]
FTIR seminar

Quantitative Analysis
FTIR Seminar
Chapter 6
Quantitative
Quantitative Handling Analysis
of Infrared Spectra
Quantitative Handling of Infrared Spectra
Interferometer
Sample
Detector
source
Light
I0 I
Absorbance : ABS=log(1/T)
d =log( I0 /I)
=ε x d x c
Transmissivity : %T=(I/I0) x 100 Ordinate axis is proportional to concentration (c)
ε : Molar extinction coefficient
d : Depth
100
c : Concentration
I0
%T
ABS
I
0 0
Transmissivity measurement Absorbance measurement

Application of Quantitative Analysis

Application of Quantitative Analysis
Key band of acrylonitrile Key band of styrene

2240cm-1: C N 1,602 cm-1
Benzene rings C=C [ Sample 1 ]
P S1
P
A1
[ Sample 2 ]
P
S2
P A2
Example: Comparison of component ratios in ABS resin

(acrylonitrile/butadiene/styrene)
FTIR seminar
JASCO FTIR Seminar Chapter

7
Infrared Spectrum Analysis
Techniques
FTIR Seminar
Chapter 7
Infrared Spectrum Analysis Techniques
FTIR seminar
Chapter 7-1
Infrared SpectrumInfrared Spectrum
Analysis Techniques Analysis Techniques
Infrared Spectrum Analysis Techniques
Overview
Substructure analysis: Analysis of functional groups
Spectrum searching: Identification of compounds
Conditions for obtaining spectra suited to analysis

Select a measurement technique which fits the analysis purpose
Optimum concentration: Low
Decrease the number of components as much as possible during preprocessing
FTIR seminar
Chapter 7-2
Infrared
Substructure Analysis Spectrum Analysis Techniques
Substructure Analysis
(1) Utilize reference material

(2) IR Mentor (application that assists the analysis of infrared spectra)
Finds the functional groups for each absorption band
Finds the functional groups for specified peaks
Finds function groups by compound type
The functional groups that have been entered are limited
FTIR seminar
Chapter 7-3
Analysis ExampleInfrared Spectrum Analysis Techniques
Analysis Example
Search example (1) : Searching by peak

FTIR seminar
Chapter 7-4
Analysis ExampleInfrared
2 Spectrum Analysis Techniques
Analysis Example 2
Search example (2): Search by compound classification

FTIR seminar
Chapter 7-5
Spectral Search Infrared Spectrum Analysis Techniques
Spectral Search
Spectral Search
(1) Compare with standard spectrum collections
(2) Compare with Sadtler databases
Important Information on Searching

Use a search algorithm suited to your purpose
Identify whether the sample is made up of single or multiple components
Judge search results by eye based on their resemblance to a pattern rather than emphasizing
evaluation points
(Algorithms can quickly find similar spectra in a large volume of data, but they cannot interpret the
spectra they find)
When there are mixtures, the key is to skillfully utilize difference spectra
Obtain other component information in advance whenever possible
FTIR seminar
Chapter 7-6
Infrared
Spectral Search Example Spectrum Analysis Techniques
Spectral Search Example

FTIR seminar
Chapter 7-7
Infrared
Spectral Search Example Spectrum
(Difference Analysis
Spectrum) Techniques
Spectral Search Example (Difference Spectrum)

Ftir

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FTIR Seminar

Chapter 1 Principles and Fundamentals of Infrared Spectroscopy

Principles and Fundamentals

Infrared absorption spectrum

Types of Electromagnetic Radiation

Interaction between Molecular Dynamics and Light

Molecular energy = electronic energy Molecular energy level

Light Emission of energy

Electronic energy .=. Visible light and ultraviolet energy

Molecular Vibration of Diatomic Molecules

Spring between two spheres

Heteronuclear diatomic molecules : HCI, CO Infrared active

Vibrational Frequency of Diatomic Molecules

f : strength constant (bond constant and bond order)

Normal Frequency of Triatomic Molecules (CO2)

CO2: linear molecule

(2) Asymmetric stretching vibration

(3) Deformation vibration

Normal Frequency of Triatomic Molecules (H2O)

(1) Symmetric stretching vibration H2O : nonlinear molecule

(2) Asymmetric stretching vibration

(3) Deformation vibration

Number of Normal Frequencies

The number of normal frequencies of a molecule consisting of n atoms can be determined by

Linear molecule 3n-5

Molecular Vibration of Polyatomic Molecules

Gamma rays X-rays Ultraviolet Visible light Infrared Microwaves

20 Methylene scissoring vibration

Deformation of the dipole moment is large : strong absorption C=O, C-X

Near-Infrared Absorption Spectrum

Spectrum shape is complex

Vibrations of heavy atoms and weak bonds

Infrared : 4,000 to 400 cm-1

Near infrared : above 4,000 cm-1

Far-infrared : below 400 cm-1

(2) Analysis targets : Organic and inorganic substances

(3) State : Gas, liquid, and solid

(4) Analysis description

Quantitative analysis is possible.

Process up to Obtaining a Spectrum

Fourier transform process

Sample Electrical system

Infrared Interference Absorption Optical Signal sampling

Electrical Digital signal IR spectrum

Intensity Distribution and Temperature Dependency versus Wavelength of

FT Optical System Diagram

Light He-Ne gas laser

Interference of Two Beams of Light

Interference Is a Superpositioning of Waves

Light source spectrum I Signal output from interference wave

(a) Monochromatic light

(b) Dichroic light

Sampling of an Actual Interferogram

Output of a Laser interferometer

Primary interferometer interferogram that was sampled

Optical path difference x

Optical path difference[x] 4000 Wavenumber[cm-1] 400

(Interferogram) (Single beam spectrum)

Time axis by FFT Wavenumber

Resolution : Fixed, qualitative analysis of liquid sample: Standard 4 cm-1

Number of integrations : Approx. ten times normal gain

Apodization function : Standard Cosine

Zero filling : Interpolation of data (smoothes out data)