Photothermal spectroscopy
Encyclopedia
Photothermal spectroscopy is a group of high sensitivity spectroscopy
techniques used to measure optical absorption and thermal characteristics of a sample. The basis of photothermal spectroscopy is the change in thermal state of the sample resulting from the absorption of radiation. Light absorbed and not lost by emission results in heating. The heat raises temperature thereby influencing the thermodynamic properties of the sample or of a suitable material adjacent to it. Measurement of the temperature, pressure, or density changes that occur due to optical absorption are ultimately the basis for the photothermal spectroscopic measurements.
As with photoacoustic spectroscopy
, photothermal spectroscopy is an indirect method for measuring optical absorption, because it is not based on the direct measure of the light which is involved in the absorption. In another sense, however, photothermal (and photoacoustic) methods measure directly the absorption, rather than e.g. calculate it from the transmission, as is the case of more usual (transmission) spectroscopic techniques. And it is this fact that gives the technique its high sensitivity, because in transmission techniques the absorptance is calculated as the difference between total light impinging on the sample and the transmitted
(plus reflected
, plus scattered
) light, with the usual problems of accuracy when one deals with small differences between large numbers, if the absorption is small. In photothermal spectroscopies, instead, the signal is essentially proportional to the absorption, and is zero when there is zero true absorption, even in the presence of reflection or scattering.
There are several methods and techniques used in photothermal spectroscopy. Each of these has a name indicating the specific physical effect measured.
that measures the change in refractive index due to heating of a medium by light. It works via a sort of "mirage
effect" where a refractive index gradient exists adjacent to the test sample surface. A probe laser beam is refracted or bent in a manner proportional to the temperature gradient of the transparent medium near the surface. From this deflection, a measure of the absorbed excitation radiation can be determined. The technique is useful when studying optically thin samples, because sensitive measurements can be obtained of whether absorption is occurring. It is of value in situations where "pass through" or transmission spectroscopy can't be used.
There are two main forms of PDS: Collinear and Transverse. Collinear PDS was introduced in a 1980 paper by A.C. Boccara, D. Fournier, et al. In collinear, two beams pass through and intersect in a medium. The pump beam heats the material and the probe beam is deflected. This technique only works for transparent media. In transverse, the probe beam heats come in normal to the surface, and the probe beam passes parallel. In a variation on this, the probe beam may reflect off the surface, and measure buckling due to heating. Transverse PDS can be done in Nitrogen, but better performance is gained in a liquid cell: usually an inert, non-absorbing material such as a perfluorocarbon is used.
In both collinear and transverse PDS, the surface is heated using a periodically modulated light source, such as an optical beam passing through a mechanical chopper or regulated with a function generator. A lock-in amplifier is then used to measure deflections found at the modulation frequency. Another scheme uses a pulsed laser as the excitation source. In that case, a boxcar average can be used to measure the temporal deflection of the probe beam to the excitation radiation. The signal falls off exponentially as a function of frequency, so frequencies around 1-10 hertz are frequently used. A full theoretical analysis of the PDS system was published by Jackson, Amer, et al. in 1981. The same paper also discussed the use of PDS as a form of microscopy, called "Photothermal Deflection Microscopy", which can yield information about impurities and the surface topology of materials.
Spectroscopy
Spectroscopy is the study of the interaction between matter and radiated energy. Historically, spectroscopy originated through the study of visible light dispersed according to its wavelength, e.g., by a prism. Later the concept was expanded greatly to comprise any interaction with radiative...
techniques used to measure optical absorption and thermal characteristics of a sample. The basis of photothermal spectroscopy is the change in thermal state of the sample resulting from the absorption of radiation. Light absorbed and not lost by emission results in heating. The heat raises temperature thereby influencing the thermodynamic properties of the sample or of a suitable material adjacent to it. Measurement of the temperature, pressure, or density changes that occur due to optical absorption are ultimately the basis for the photothermal spectroscopic measurements.
As with photoacoustic spectroscopy
Photoacoustic spectroscopy
Photoacoustic spectroscopy is the measurement of the effect of absorbed electromagnetic energy on matter by means of acoustic detection. The discovery of the photoacoustic effect dates to 1880 when Alexander Graham Bell showed that thin discs emitted sound when exposed to a beam of sunlight that...
, photothermal spectroscopy is an indirect method for measuring optical absorption, because it is not based on the direct measure of the light which is involved in the absorption. In another sense, however, photothermal (and photoacoustic) methods measure directly the absorption, rather than e.g. calculate it from the transmission, as is the case of more usual (transmission) spectroscopic techniques. And it is this fact that gives the technique its high sensitivity, because in transmission techniques the absorptance is calculated as the difference between total light impinging on the sample and the transmitted
Transmittance
In optics and spectroscopy, transmittance is the fraction of incident light at a specified wavelength that passes through a sample. A related term is absorptance, or absorption factor, which is the fraction of radiation absorbed by a sample at a specified wavelength...
(plus reflected
Reflection (physics)
Reflection is the change in direction of a wavefront at an interface between two differentmedia so that the wavefront returns into the medium from which it originated. Common examples include the reflection of light, sound and water waves...
, plus scattered
Diffuse reflection
Diffuse reflection is the reflection of light from a surface such that an incident ray is reflected at many angles rather than at just one angle as in the case of specular reflection...
) light, with the usual problems of accuracy when one deals with small differences between large numbers, if the absorption is small. In photothermal spectroscopies, instead, the signal is essentially proportional to the absorption, and is zero when there is zero true absorption, even in the presence of reflection or scattering.
There are several methods and techniques used in photothermal spectroscopy. Each of these has a name indicating the specific physical effect measured.
- Photothermal lens spectroscopy (PTS or TLS) measures the thermal blooming that occurs when a beam of light heats a transparent sample. It is typically applied for measuring minute quantities of substances in homogeneous gas and liquid solutions.
- Photothermal deflection spectroscopy (PDS), also called the mirageMirageA mirage is a naturally occurring optical phenomenon in which light rays are bent to produce a displaced image of distant objects or the sky. The word comes to English via the French mirage, from the Latin mirare, meaning "to look at, to wonder at"...
effect, measures the bending of light due to optical absorption. This technique is particularly useful for measuring surface absorption and for profiling thermal properties in layered materials. - Photothermal diffraction, a type of four wave mixing, monitors the effect of transient diffraction gratingDiffraction gratingIn optics, a diffraction grating is an optical component with a periodic structure, which splits and diffracts light into several beams travelling in different directions. The directions of these beams depend on the spacing of the grating and the wavelength of the light so that the grating acts as...
s "written" into the sample with coherent lasers. It is a form of real-time holographyHolographyHolography is a technique that allows the light scattered from an object to be recorded and later reconstructed so that when an imaging system is placed in the reconstructed beam, an image of the object will be seen even when the object is no longer present...
. - Photothermal emission measures an increase in sample infraredInfraredInfrared 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...
radianceRadianceRadiance and spectral radiance are radiometric measures that describe the amount of radiation such as light or radiant heat that passes through or is emitted from a particular area, and falls within a given solid angle in a specified direction. They are used to characterize both emission from...
occurring as a consequence of absorption. Sample emission follows Stefan's law of thermal emission. This methods is used to measure the thermal properties of solids and layered materials.
Photothermal deflection spectroscopy
Photothermal deflection spectroscopy is a kind of spectroscopySpectroscopy
Spectroscopy is the study of the interaction between matter and radiated energy. Historically, spectroscopy originated through the study of visible light dispersed according to its wavelength, e.g., by a prism. Later the concept was expanded greatly to comprise any interaction with radiative...
that measures the change in refractive index due to heating of a medium by light. It works via a sort of "mirage
Mirage
A mirage is a naturally occurring optical phenomenon in which light rays are bent to produce a displaced image of distant objects or the sky. The word comes to English via the French mirage, from the Latin mirare, meaning "to look at, to wonder at"...
effect" where a refractive index gradient exists adjacent to the test sample surface. A probe laser beam is refracted or bent in a manner proportional to the temperature gradient of the transparent medium near the surface. From this deflection, a measure of the absorbed excitation radiation can be determined. The technique is useful when studying optically thin samples, because sensitive measurements can be obtained of whether absorption is occurring. It is of value in situations where "pass through" or transmission spectroscopy can't be used.
There are two main forms of PDS: Collinear and Transverse. Collinear PDS was introduced in a 1980 paper by A.C. Boccara, D. Fournier, et al. In collinear, two beams pass through and intersect in a medium. The pump beam heats the material and the probe beam is deflected. This technique only works for transparent media. In transverse, the probe beam heats come in normal to the surface, and the probe beam passes parallel. In a variation on this, the probe beam may reflect off the surface, and measure buckling due to heating. Transverse PDS can be done in Nitrogen, but better performance is gained in a liquid cell: usually an inert, non-absorbing material such as a perfluorocarbon is used.
In both collinear and transverse PDS, the surface is heated using a periodically modulated light source, such as an optical beam passing through a mechanical chopper or regulated with a function generator. A lock-in amplifier is then used to measure deflections found at the modulation frequency. Another scheme uses a pulsed laser as the excitation source. In that case, a boxcar average can be used to measure the temporal deflection of the probe beam to the excitation radiation. The signal falls off exponentially as a function of frequency, so frequencies around 1-10 hertz are frequently used. A full theoretical analysis of the PDS system was published by Jackson, Amer, et al. in 1981. The same paper also discussed the use of PDS as a form of microscopy, called "Photothermal Deflection Microscopy", which can yield information about impurities and the surface topology of materials.
External links
- Quantities, terminology, and symbols in photothermal and related spectroscopies (IUPAC Recommendations 2004)
- on-line version Chapter 1 of Stephen E. Bialkowski's Photothermal Spectroscopy Methods for Chemical Analysis John Wiley, New York 1996
- The Group of Thermooptical Spectroscopy of Dr. M. Proskurnin
- International Photoacoustic and Photothermal Association
- photonics site