Fourier Transform Infrared

(FT-IR) Microspectroscopy
Methods and Applications
 Infrared Microspectroscopy

Who uses it?

– Polymers
– Pharmaceuticals
– Forensics
– General Chemicals
– Electronics
– Metals Manufacturing
 Infrared Microspectroscopy

What can it help them do?

– Chemical ID
– Incoming/Outgoing QA/QC
– Quantitative Analysis
– Corrosion and Weathering Studies
– Aids to Research and Development
– Process Analysis
 Infrared Microanalysis

• Various accessories are available for

microanalysis applications: micro-ATR’s,
diamond compression cells or beam
condensors.
• Microanalysis is performed for samples on the
order of 1 mm or less: single fibers, organic
crystals, paint chips or polymers, etc.
• A very common accessory for microanalysis is
an FT-IR microscope system.
 Infrared Microanalysis

• The first infrared microscope system was built for a

dispersive instrument in the late 1950's. It was a
failure, however, as the accessory had insufficient
throughput to provide much more capability than a
simple beam condenser of the day.
• Infrared microscopes did not appear again until the
mid-to-late 1970's, when the power of the FT-IR
spectrometer allowed for higher throughputs and
greater signal-to-noise for micro-sampling
applications.
 The FT-IR Microscope System

• Infrared microscope systems are a compromise

between a desire for the clarity of a refractive optical
system using lenses and the necessity of using a
reflective optical system containing mirrors.
• Simple and reliable Cassegrain objective and
condenser pairs provide the beam condensation
needed for infrared microscopy without the
aberrations of parabolic mirrors. Visible and infrared
light paths combine prior to the cassegrain optics,
providing excellent visualization capability.
 The Cassegrain Reflecting Optic

Collimated infrared beam

The cassegrain optic
Secondary mirror
provides high orders of
magnification with a
minimum of distortion
Primary or aberration. The
mirror optical system produces
Working a focal plane, the
Distance
dimensions controlled
Sample
by the slit system.
The Cassegrain Reflecting Optic

Two cassegrains are used together,

one to condense, the other to ‘de-
magnify’ the infrared light after it
passes through the sample. The
focal planes of the cassegrains are
matched to examine the sample in
transmittance. In reflectance mode,
half the objective cassegrain is used
to bring the beam to the sample, the
other half used to direct the
reflectance information onto the
detector.
 Visible Illumination
Transmission Reflection
 The Microscope Aperture

• The aperture is used to control the spatial position and

size of the sample exposed to the infrared light.
• Either a single or dual aperture can be used, system
optical considerations will determine the proper
position for the aperture at a reciprocal focal point to
the cassegrain system.
• The primary criterion for an aperture system is the
ability to exclude areas outside the sample of interest;
the final spectrum should only display data resulting
from the sample area of interest.
Laminate Layer - Nylon
Sample Aperture – Spatial Resolution

Polymer Laminate - 10 mm layer illuminated

 Infrared Spatial Resolution
Laminate Spectra
70
%T

60
30 mm Layer - polyvinyl chloride

60
%T

40
10 mm Layer - polyvinylidene fluoride (plasticized)
20

80
60
%T

40
Large Layer - polyvinylidene fluoride
20

4000 3500 3000 2500 2000 1500 1000

Wavenumbers (cm-1)
Applications of FT-IR Microspectroscopy

• Failure/Defect Analysis of Laminates, Coatings

and Paints
• QC/QA on Select Sample Sites
• Pharmaceutical/Biochemical Research
• Limited Sample Analysis Problems
• Forensics
• Product Development, Reverse Engineering
• Chemical Mapping
 FT-IR Microspectroscopy

• Sampling Applications
– Solids or discrete particles
– Sample size: ~12 to 250 microns (larger
samples may be used, especially for mapping or
'imaging' experiments)
– Transmission; diffuse, specular/grazing angle or
micro-ATR analysis methods
– Sensitive to component concentrations  0.01%
 FT-IR Microspectroscopy

• Transmission Microspectroscopy
 Fibers, laminates, and thin films
Transmission - Human Epithelial Cell

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0
4000 3500 3000 2500 2000 1500 1000

Wavenumbers (cm-1)
Transmission - Single Fiber in Compression Cell
0.22
0.20 Orlon Fiber
0.18

0.16
0.14
Absorbance

0.12
0.10
0.08
0.06
0.04

0.02
0.00
3500 3000 2500 2000 1500 1000

Wavenumbers (cm-1)
Transmission Microspectroscopy
Fiber Analysis by Transmission Microspectroscopy
Laminate Layer - Nylon
Laminate Layer
Polymer Laminates
Laminate Analysis
Polymer Laminate - 50 micron layer
Polymer Laminate - 25 micron layer
Polymer Laminate Cross Section
Polymer Laminate - Spectra of Individual Layers
100

50
PET

50
EVA

100

50
PE

20
Cellulose

4000 3500 3000 2500 2000 1500 1000

Wavenumbers (cm-1)
Simple Samples - Transmission Spectra
Print Roller Contamination
 FT-IR Microspectroscopy

• Reflectance Microspectroscopy
 Specular, Reflection-Absorption, Grazing
Angle and Diffuse
 Specular Reflection
1.0 Polymethyl methacrylate after KK Transformation

0.8

0.6

0.4

0.2

Polymethyl methacrylate specular reflectance

10

8
%T

3500 3000 2500 2000 1500 1000

Wavenumbers (cm-1)
 Polymer Film on Al

100 mm
 Reflection-Absorption
Polymer Film on Al
1.4
1.3 Polyvinyl acetate with additive
1.2
1.1
1.0
Log(1/R)

0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
3500 3000 2500 2000 1500 1000

Wavenumbers (cm-1)
Reflection-Absorption Spectroscopy
Grazing Angle Analysis of Printed Circuit Board (PCB)
Solder Mask

 Problem: analyze coating

thickness applied to PCB
circuit contact pads (large
rectangular contacts are
100 x 150 microns).
 Answer: grazing-angle
analysis of monolayer
coating and follow peak
height(s) of coating peaks.
Grazing Angle Spectrum of PCB Coating
Least Squares Plot of Peak Height vs. Thickness
Coating Thickness vs. Peak Height

0.025

0.023 y = 0.0268x + 0.0099

R2 = 0.9978

0.021
Peak Height

Series1
Linear (Serie

0.019

0.017

0.015
0 0.1 0.2 0.3 0.4 0.5 0.6
Coating Thickness
 Diffuse Reflectance
Tetracyclene Hydrochloride - Diffuse Reflectance
0.7

0.6

0.5
Log(1/R)

0.4

0.3

0.2

0.1

0.0
4000 3500 3000 2500 2000 1500 1000

Wavenumbers (cm-1)
Corrected Diffuse Reflection Spectra of Toner Samples
(Kubelka Munk Correction Specific to Diffuse Reflectance Spectra)
Spectral Display Features - Comparison of Data
 ATR Objective

• Variety of ATR Crystals - ZnSe, Ge, and Si for

widest choice of penetration depth
• Surface Sampling (0.4 - 8.0 um)
• Ideal for non-destructive analysis of samples
• ATR pressure sensor option for repeatable
pressure and reliable results
Cross Section - Paint Layers

100 mm
 ATR Microscopy of Paint Layers
0.4
Red layer
0.2

0.0

Brown layer
0.4

0.2

0.4 White layer

0.2

0.0
4000 3500 3000 2500 2000 1500 1000

Wavenumbers (cm-1)
 ATR Microscopy - Soiled Carpet
0.6 Carpet - Nylon 6,6 Fibers
Absorbance

0.5
0.4
0.3
0.2
0.1

0.3
Soiled Area - “Oil”
Absorbance

0.2

0.1

0.0

3500 3000 2500 2000 1500 1000

Wavenumbers (cm-1)
 ATR Microscopy - Hard Material
1.4
1.3
Polycarbonate by ATR Diamond crystal
1.2
1.1
1.0
Absorbance

0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
3500 3000 2500 2000 1500 1000

Wavenumbers (cm-1)
Blade Strip Sample -
Micro-ATR Analysis (ZnSe crystal)
 Mapping and Imaging Applications

 The addition of an automated stage and

mapping software to an infrared
microscope system provides a ‘mapping’
capability.
 Discrete sampling points are examined
using the stage to move the sample.
Autofocusing capability is desirable to
conform to the sample topography.
 Processing of the sample data can provide
an ‘image’ of the spectral data based on
peak location, height, area, etc.
 Mapping a blended polymer sample

Y (mm)

X (mm)
Specific infrared peak ratios used to structurally image
the sample
 Mapping and Imaging Applications

 Imaging systems do not examine a sample based

on spectral collection from discrete spatial
points, but rather collect data from the sample as
a composite image.
 Sample information is, generally, processed by
an array detector for the FT-IR.
 Imaging data can have lower spatial or spectral
resolution compared to discrete mapping data.
 Discrete sampling techniques (transmittance,
reflectance, etc.) can be used in imaging and
mapping experiments.
 IR Imaging
Transmittance measurement A
of multi-layer film
Measurement area: 600 x 600 µm
Number of measurement points: 48 x 48
Spatial resolution: 12.5 x 12.5 µm
Resolution: 16 cm-1
Accumulations: 16
B C
B
2

A
C

1
Abs

D E
E
D

-0.1
4000 3000 2000 1000 750
Wavenumber [cm-1]
 Nylon Fiber
1.4
37 37

• 656 spectra
• 200 x 500 microns -100 -100

Y [um]
Y [um]
-200 -200

-300 -300

-400 -400
-463 -463
428 500 615.5 428 500 615.5
X [um] X [um] -0.1
Nylon Fiber
 3D Spectra

1.4

1
Abs
0.5
615.5
-0.1
4000 3000 428
X [um]
Wavenumber [cm-1] 2000 750
Polymer Laminate
 Polymer Laminate
1.1 0.19
830.5 1.1 0
830.5 830.5

600
600 600

Y [um]
Y [um]
Y [um]

400
400 400

200
200
200
43
43 811 1000 1198.5
811 1000431198.5
1 1000 1198.5 X [um] -0
X [um]811 1000 1198.5-0.1
X [um] -0.1
• 2048 spectra X [um] -0.04
• 380 x 800 microns
Ink Spots on Mirror
 Ink Spots on Mirror

• 11136 spectra
• 1188 x 1438 microns
 Ink Spots on Mirror

• 8827 spectra
• 1125 x 1200 microns
Ink Spots on Mirror
 Silicon Chip

1.5

Abs

0.5

0.2
4000 3000 2000 750
Wavenumber [cm-1]

• 2304 spectra
• 588 x 588 microns
Silicon Chip
What is it?
 Skin Cells (Inner Cheek)

0.4

0.3

0.2

Abs
0.1

-0.1
4000 3000 2000 750
Wavenumber [cm-1]

• 3111 spectra
• 750 x 625 microns
 Skin Cells (Inner Cheek)

0.4

0.3

0.2

Abs
0.1

-0.1
4000 3000 2000 750
Wavenumber [cm-1]

• 18495 spectra
• 1675 x 1700 microns
 Automobile Paint Chip
8 layer paint chip from an automobile was measured by IMV-4000. Spectra can
be obtained (and further analyzed) at any point from the image.

Visible image IR Imaging

Spectra of each layer

Resolution: 16 cm-1
Accumulation: 16
 Sampling Application Problem
• A number of sampling methods are required to
analyze component failures.
– Customer supplied 3 circuit boards including 1 new
PCB without components.
– The objective: collect spectra from various points on
the PCB and identify any contaminants or other
problems.
– The data collection was simple, the interpretation
was more difficult because many of the compounds
used are proprietary in nature and are not available
in commercial libraries.
Visual Picture of Printed Circuit Board (PCB)
Solder Mask on Copper Lead
IC Crystal Contamination
Contamination of Circuit Connection Point
Contamination of Circuit Connection Point
Contamination of Solder Joint
Contamination of Raised IC Contacts
Circuit Contact Contamination - Transmission
Microscopy
Circuit Contact Contaminant - Transmission
Microscopy
 FT-IR Microspectroscopy

• Microanalysis can be used for a wide

variety of samples.
• Transmission and reflection analysis
methods can be used.
• Sample sizes range from 20 micron to
whatever can fit onto the microscope stage.