Attenuated total reflectance
Encyclopedia
Attenuated total reflectance (ATR) is a sampling technique used in conjunction with infrared spectroscopy
which enables samples to be examined directly in the solid
, liquid
or gas
state without further preparation.
ATR uses a property of total internal reflection
resulting in an evanescent wave
. A beam of infrared
light
is passed through the ATR crystal in such a way that it reflects at least once off the internal surface in contact with the sample. This reflection forms the evanescent wave which extends into the sample. The penetration depth into the sample is typically between 0.5 and 2 micrometre
s, with the exact value being determined by the wavelength of light, the angle of incidence and the indices of refraction for the ATR crystal and the medium being probed. The number of reflections may be varied by varying the angle of incidence. The beam is then collected by a detector as it exits the crystal. Most modern infrared spectrometers can be converted to characterise samples via ATR by mounting the ATR accessory in the spectrometer's sample compartment. The accessibility of ATR-FTIR
has led to substantial use by the scientific community.
This evanescent effect only works if the crystal is made of an optical material with a higher refractive index
than the sample being studied. Otherwise light is lost to the sample. In the case of a liquid sample, pouring a shallow amount over the surface of the crystal is sufficient. In the case of a solid sample, it is pressed into direct contact with the crystal. Because the evanescent wave into the solid sample is improved with a more intimate contact, solid samples are usually firmly clamped against the ATR crystal, so that trapped air is not the medium through which the evanescent wave travels, as that would distort the results.
Typical materials for ATR crystals include germanium
, KRS-5
and zinc selenide
, while silicon
is ideal for use in the Far-IR region of the electromagnetic spectrum
. The excellent mechanical properties of diamond
make it an ideal material for ATR, particularly when studying very hard solids, but its much higher cost means it is less widely used. The shape of the crystal depends on the type of spectrometer and nature of the sample. With dispersive
spectrometers, the crystal is a rectangular slab with chamfered edges, seen in cross-section in the illustrations. With FTIR cylindrical crystals are used with liquid samples.
in forensic science.
Infrared spectroscopy
Infrared spectroscopy is the spectroscopy that deals with the infrared region of the electromagnetic spectrum, that is light with a longer wavelength and lower frequency than visible light. It covers a range of techniques, mostly based on absorption spectroscopy. As with all spectroscopic...
which enables samples to be examined directly in the solid
Solid
Solid is one of the three classical states of matter . It is characterized by structural rigidity and resistance to changes of shape or volume. Unlike a liquid, a solid object does not flow to take on the shape of its container, nor does it expand to fill the entire volume available to it like a...
, liquid
Liquid
Liquid is one of the three classical states of matter . Like a gas, a liquid is able to flow and take the shape of a container. Some liquids resist compression, while others can be compressed. Unlike a gas, a liquid does not disperse to fill every space of a container, and maintains a fairly...
or gas
Gas
Gas is one of the three classical states of matter . Near absolute zero, a substance exists as a solid. As heat is added to this substance it melts into a liquid at its melting point , boils into a gas at its boiling point, and if heated high enough would enter a plasma state in which the electrons...
state without further preparation.
ATR uses a property of total internal reflection
Total internal reflection
Total internal reflection is an optical phenomenon that happens when a ray of light strikes a medium boundary at an angle larger than a particular critical angle with respect to the normal to the surface. If the refractive index is lower on the other side of the boundary and the incident angle is...
resulting in an evanescent wave
Evanescent wave
An evanescent wave is a nearfield standing wave with an intensity that exhibits exponential decay with distance from the boundary at which the wave was formed. Evanescent waves are a general property of wave-equations, and can in principle occur in any context to which a wave-equation applies...
. A beam of infrared
Infrared
Infrared light is electromagnetic radiation with a wavelength longer than that of visible light, measured from the nominal edge of visible red light at 0.74 micrometres , and extending conventionally to 300 µm...
light
Light
Light or visible light is electromagnetic radiation that is visible to the human eye, and is responsible for the sense of sight. Visible light has wavelength in a range from about 380 nanometres to about 740 nm, with a frequency range of about 405 THz to 790 THz...
is passed through the ATR crystal in such a way that it reflects at least once off the internal surface in contact with the sample. This reflection forms the evanescent wave which extends into the sample. The penetration depth into the sample is typically between 0.5 and 2 micrometre
Micrometre
A micrometer , is by definition 1×10-6 of a meter .In plain English, it means one-millionth of a meter . Its unit symbol in the International System of Units is μm...
s, with the exact value being determined by the wavelength of light, the angle of incidence and the indices of refraction for the ATR crystal and the medium being probed. The number of reflections may be varied by varying the angle of incidence. The beam is then collected by a detector as it exits the crystal. Most modern infrared spectrometers can be converted to characterise samples via ATR by mounting the ATR accessory in the spectrometer's sample compartment. The accessibility of ATR-FTIR
Fourier transform infrared spectroscopy
Fourier transform infrared spectroscopy is a technique which is used to obtain an infrared spectrum of absorption, emission, photoconductivity or Raman scattering of a solid, liquid or gas. An FTIR spectrometer simultaneously collects spectral data in a wide spectral range...
has led to substantial use by the scientific community.
This evanescent effect only works if the crystal is made of an optical material with a higher refractive index
Refractive index
In optics the refractive index or index of refraction of a substance or medium is a measure of the speed of light in that medium. It is expressed as a ratio of the speed of light in vacuum relative to that in the considered medium....
than the sample being studied. Otherwise light is lost to the sample. In the case of a liquid sample, pouring a shallow amount over the surface of the crystal is sufficient. In the case of a solid sample, it is pressed into direct contact with the crystal. Because the evanescent wave into the solid sample is improved with a more intimate contact, solid samples are usually firmly clamped against the ATR crystal, so that trapped air is not the medium through which the evanescent wave travels, as that would distort the results.
Typical materials for ATR crystals include germanium
Germanium
Germanium is a chemical element with the symbol Ge and atomic number 32. It is a lustrous, hard, grayish-white metalloid in the carbon group, chemically similar to its group neighbors tin and silicon. The isolated element is a semiconductor, with an appearance most similar to elemental silicon....
, KRS-5
Thallium halides
The thallium halides include monohalides, where thallium has oxidation state +1, trihalides where thallium generally has oxidation state +3 and some intermediate halides with mixed +1 and +3 oxidation states.- Monohalides :...
and zinc selenide
Zinc selenide
Zinc selenide , is a light yellow binary solid compound. It is an intrinsic semiconductor with a band gap of about 2.70 eV at 25 °C. ZnSe rarely occurs in nature...
, while silicon
Silicon
Silicon is a chemical element with the symbol Si and atomic number 14. A tetravalent metalloid, it is less reactive than its chemical analog carbon, the nonmetal directly above it in the periodic table, but more reactive than germanium, the metalloid directly below it in the table...
is ideal for use in the Far-IR region of the electromagnetic spectrum
Electromagnetic spectrum
The electromagnetic spectrum is the range of all possible frequencies of electromagnetic radiation. The "electromagnetic spectrum" of an object is the characteristic distribution of electromagnetic radiation emitted or absorbed by that particular object....
. The excellent mechanical properties of diamond
Diamond
In mineralogy, diamond is an allotrope of carbon, where the carbon atoms are arranged in a variation of the face-centered cubic crystal structure called a diamond lattice. Diamond is less stable than graphite, but the conversion rate from diamond to graphite is negligible at ambient conditions...
make it an ideal material for ATR, particularly when studying very hard solids, but its much higher cost means it is less widely used. The shape of the crystal depends on the type of spectrometer and nature of the sample. With dispersive
Dispersion (optics)
In optics, dispersion is the phenomenon in which the phase velocity of a wave depends on its frequency, or alternatively when the group velocity depends on the frequency.Media having such a property are termed dispersive media...
spectrometers, the crystal is a rectangular slab with chamfered edges, seen in cross-section in the illustrations. With FTIR cylindrical crystals are used with liquid samples.
Applications
Infrared (IR) spectroscopy by ATR is applicable to the same chemical or biological systems as the transmission method. One advantage of ATR-IR over transmission-IR, is the limited path length into the sample. This avoids the problem of strong attenuation of the IR signal in highly absorbing media, such as aqueous solutions. Recently, ATR-IR has been applied to microfluidic flows of aqueous solutions by engineering microreactors with built in apertures for the ATR crystal, allowing the flow within microchannels to pass across the crystal surface for characterisation. The ability to passively characterise samples, with no sample preparation has also lead to the use of ATR-FTIR in studying trace evidenceTrace evidence
Trace evidence is evidence that occurs when different objects contact one another. Such materials are often transferred by heat induced by contact friction....
in forensic science.