Attenuated Total
Reflectance-FTIR
Spectroscopy
FT-IR Reflection Techniques
Internal Reflection Spectroscopy:
Attenuated Total Reflection (ATR)
External Reflection Spectroscopy:
Specular Reflection (smooth surfaces)
Combination of Internal and External Reflection:
Diffuse Reflection (DRIFTs) (rough surfaces)
Introduction
Internal Reflection Spectroscopy
Infrared beam reflects from a interface via total internal
reflectance
a versatile and powerful technique which enables
samples to be examined directly in the solid or liquid
state.
It allows very thin sampling path length and depth of
penetration of the IR beam into the sample.
Useful for samples that are too thick to be analysed by
transmission and those that strongly absorb radiation.
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WHAT IS ATR?
The infrared radiation interacts with the sample through a series of
standing waves, called as evanescent waves.
An evanescent wave is a penetrating electromagnetic field whose
intensity quickly decays as it moves away from its source.
An evanescent beam interacts with the sample, sample absorbs
energy.
Thus there is reduction in the intensity of the reflected wave
reaching the detector.
How it works
Data collection
When collecting ATR data, samples are run as
%reflectance (equivalent to absorbance) or log
(1/R).
Reflection Absorption Spectrum of Hydroxyapatite / Fibrinogen Multi-Layer Thin Film on Gold Plating
FACTORS AFFECTING ATR ANALYSIS
Refractive indices of the ATR crystal (IRE) and the sample
Angle of incidence of the IR beam (Ɵ)
Depth of penetration (dp)
Wavelength of the IR beam- (λ)
Number of reflections
Quality of the sample contact with ATR crystal
ATR crystal characteristic
*When an incident ray is totally internally reflected at the interface between
two materials of different refractive index, the intensity of the evanescent
field extending into the medium of lower index decays exponentially with
distance from the boundary: Iev = Io exp [-z/dp]
– z is the distance normal to the optical interface,
– Io is the intensity at z = 0,
– dp is the penetration depth
Depth of penetration of the infrared beam into the
sample depends on λ, nsmp, nIRE, Ɵ
The dP of the spectrum collected varies
with the wavelength of the radiation:
-longer λ, greater dP
-dP lower at higher wavenumbers
-ATR intensities decreased at
higher wavenumbers if compared to transmission spectra
Critical Angle depends on nIRE and nsmp
•increasing nIRE =˃ decreasing Ɵ and dP
•high values of nIRE needed
Instrumentation
Continued
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Instrumentation
• IR radiation passes through an IR transmitting crystal of
high refractive index, greater than that of the sample,
thus allowing radiation to reflect in the crystal one or
more times
• When the refractive index of the prism is greater than
that of the sample medium, and if the angle, Ѳ is
greater than the critical angle, the IR beam suffers a
total internal reflectance
• Attenuated total reflection accessory measures the
totally reflected infrared beam when the beam comes
and contact with a sample
CRYSTAL MATERIALS
MATERIAL ATR SPECTRA REFRACTIV DEPTH OF USES
RANGE (cm-1) E INDEX PENETRATION (μm)
(at 45° & 1000 cm-1)
Germanium 5,500-675 4 0.66 Good for most samples.
Strong absorbing
samples, such as dark
polymers
Silicone 8,900- 1,500 3.4 0.85 Resistant to basic
and 360-120 solutions
AMTIR 11,000-725 2.5 1.77 Very resistant to acidic
(amorphous material solutions, performs well
transmitting
IR,contains arsenic &
in pH 1-9
selenide)
ZnSe 15,000-650 2.4 2.01 General use
Diamond 25,000-100 2.4 2.01 Good for most samples.
Extremely caustic or
harder samples.
Germanium (Ge)
high refractive index,
used when analyzing samples that have high refractive
indices
Silicon (Si)
hard and brittle, chemically inert, affected only by strong
oxidizers
well suited for applications requiring temperature changes
as it withstands thermal shocks better then other ATR
materials
hardest crystal material offered except for Diamond, which
makes it well suited for abrasive samples that might
otherwise scratch softer crystal materials
below 1500 cm-1 usefulness limited
Zinc Selenide ZnSe
preferred for all routine applications, limited use with
strong acids and alkalies
surface etched during prolonged exposure to extremes of
pH, complexing agents (ammonia and EDTA) will also erode
its surface because of the formation of complexes with the
zinc
AMTIR
as a glass from selenium, germanium and arsenic
insolubility in water
similar refractive index to that of zinc selenide
can be used in measurements that involve strong acids
Diamond
for analysis of a wide range of samples, including acids,
bases, and oxidizing agents
scratch and abrasion resistant, expensive
intrinsic absorption from approximately 2300 -1800 cm-1
limits its usefulness in this region (5% transmission)
Single Bounce ATR Multi-Bounce ATR
Small sampling area Broad sampling area provides
use for strong absorbers - - greater contact with the sample
solid samples, liquids - use for weak absorbers or
dilute solutions
For thin films, the ATR spectra are the same as
transmission spectra.
For thick films, the absorption bands are more intense
at longer wavelengths.
As the angle of incidence approaches the critical angle,
the bands tend to broaden on the long wavelength side
and the minima are displaced to longer wavelengths
(lower wavenumbers).
Dispersion type spectra are observed very close to and
below critical angle.
Applications
Solid Analysis Liquid Analysis Powder Analysis
excellent technique for analyze non-aqueous easier to run by ATR than
measuring the solutions by IR transmission,
composition of solids because little or no
preparation is required
ideal technique for Cleanup is easy and fast pure samples and mixtures
measuring dark colored that are available in
materials which often powdered from
absorb too much energy to
be measured by IR
transmission
films, fabrics, paper, hard lubricants, oils, paints, pharmaceuticals and
polymer sheets, glass, glues, solvents, inks and pigments
rubber dyes,
Gels and pastes can also
be analyzed
Advantages
• Little or no sample preparation
• Very thin sampling path length
• Faster sample analysis (<1 minute for thick samples)
• Cleanup is easy and fast.
• Versatile and non-destructive technique for the analyses
of a variety of materials: soft solid materials, liquids,
powder, gels, pastes, surface layers, polymer films oils,
lubricants, paints, glues, solvents.
• Useful for surface characterization, opaque samples
Disadvantages
• The ATR crystal absorbs energy at lower
energy levels (longer wavelengths)
• If the sample does not have good contact with
the crystal, the data will not be accurate
• Most ATR crystals have pH limitations
• Limitations: sensitivity is typically 3-4 orders
less than transmission
