The Photoacoustic Effect

Benjamin T. Spike Physics 325 April 21, 2006

The photoacoustic effect is a conversion between light and acoustic waves due to absorption and localized thermal excitation. When rapid pulses of light are incident on a sample of matter, they can be absorbed and the resulting energy will then be radiated as heat. This heat causes detectable sound waves due to pressure variation in the surrounding medium. With the invention of the microphone and laser, the photoacoustic effect took on new life as an important tool in spectroscopic analysis and continues to be applied in an increasing number of fields. The photoacoustic effect was first discovered by Alexander Graham Bell in his search for a means of wireless communication.1 Bell succeeded in transmitting sound with an invention he called the photophone, which carried a vocal signal with a beam of sunlight that was reflected by a vocally modulated mirror. [Fig. 1] The sound could be recovered with an ordinary telephone receiver connected to a selenium cell illuminated by the light. Bell published the results in a presentation to the American Association for the Advancement of Science in 1880.

Figure 1 The photophone. (From Lscher, reproduced from Bell, 1880) In working with the photophone, Bell was surprised to discover that a sound wave could be produced directly from a solid sample if the incident light was rapidly interruptedtypically on the order of kHz. Bell used a spinning slotted wheel to mechanically chop the incident sunlight at this frequency. He observed that the

resulting acoustic signal is dependent on the composition of the sample and correctly conjectured that the effect was caused by absorption of the incident light. Recognizing that the photoacoustic effect had applications in spectroscopy, Bell developed the spectrophone, essentially an ordinary spectroscope equipped with a hearing tube instead of an eyepiece. [Fig. 2] Samples could then be analyzed by sound when a source of light was applied. As noted by Bell, the ear cannot of course compete with the eye for accuracy2 when examining the visible spectrum. However, the spectrophone provided a means for measuring spectra beyond the visible regime that were previously undetectable.

Figure 2 The spectrophone. (From Lscher, reproduced from Bell, 1880) Bells initial experiments focused on the solid phase of matter, but John Tyndall and Wilhelm Roentgen performed subsequent experiments demonstrating the same effect in liquids and gases. Tyndall was the first to discover that the intensity of the produced sound was directly proportional to the amount of heat absorbed, or equivalently, the intensity of the applied light.3 For the most part, these initial observations were entirely qualitative since the ability to reliably quantify and compare the intensity of sound did not yet exist. While the photoacoustic effect enjoyed a great wave of enthusiasm in the years immediately following Bells initial discovery in 1880, its application to spectroscopy

quickly died down and no such experiments were performed for over half a century. This was largely due to a lack of intense light sources and precise means of measurement during Bells time. In 1938, M. L. Viengerov was the first to revive the use of the photoacoustic effect in gas analysis, which proved to be its most widespread application in the following decades.4 Viengerov was able to measure CO2 concentrations in N2 gas to about 0.2% by volume. However, his results were affected by the relatively low sensitivity of his microphone as well as undesired photoacoustic effects from the glass chamber, a problem that persists in modern photoacoustic analysis. The development of the laser in the early 1970s had critical implications for photoacoustic spectroscopy. Lasers provided high intensity light at a tunable frequency, which allowed an increase in sound amplitude and sensitivity. To this end, photoacoustics was able to be applied across a broader range of fields. For example, some of the first physical measurements of ozone depletion due to nitric oxide emission were made in the early seventies with a photoacoustic detector carried by a balloon.

(a)

(b)

(c)

(d)

Figure 3 Visualization of the photoacoustic effect (Provided by the author) The mechanics of the photoacoustic effect can be envisioned as a series of steps. [Fig. 3] First, pulsed light that is incident on a sample is absorbed (a) and the constituent molecules become thermally excited (b). Periodic heat flow from the sample to the surrounding gas causes pressure waves (c) that are in turn detected by an acoustic sensor

(d). The pressure waves are characteristic of the sample and are used to determine composition, concentration, and other thermophysical properties. The most commonly employed model for describing the photoacoustic effect in condensed samples was developed in the 1970s by Rosencwaig and Gersho.5 Applying Beers Law with radiation intensity I0 and optical absorption coefficient :

dI = " ! I dx # I = I 0 e " !x
Suppose the incident radiation is modulated with frequency . Then the incident intensity is given by:

1 I " = I(1# cos$t) 2

The sample and the gas must each satisfy the heat-diffusion equation, which for the case of the sample is given by:

" T 1 "T %& rt I ' 1 "T %& rt I0 $ %x = $ = $ e (1$ cos(t) "x 2 # "t k # "t 2k
where " rt is the probability of radiationless transition, and thermal diffusivity " =

#c

!
!

where k is thermal conductivity of the sample, " is the density, and c is the specific

! heat. Rosencwaig and Gersho determined the following equation for temperature in the
! surrounding medium as a function of ! position and time: both

T ac ( x, t ) = e ! ax [#1 cos("t + ax) ! # 2 sin("t + ax)]

where the complex temperature amplitude " = "1 + i" 2 , and thermal diffusion coefficient
a=

" . 2#

The equation describes a periodic wave of temperature that propagates through the medium surrounding the sample. The temperature fluctuation described by this equation is the cause of the pressure waves that are detected. Since the e"ax causes the wave to decay away from the sample, the sensor should be located within the thermal diffusion length =
! 1 2" in order to maximize the strength of the acoustic signal. = a #

Surprisingly, modern photoacoustic analysis has not deviated far from Bells
! original chopped light setup, apart from the introduction of lasers and microphones. A

typical photoacoustic experiment consists of a laser incident upon a chamber, which is modulated with a physical chopper or some other method of precisely pulsing the light. The acoustic signal is measured with either a microphone or piezo sensor depending on the frequency. Frequencies of applied light from microwaves to X-rays can be used, but lasers or xenon lamps tend to be the most common. Sensitivity is of great importance in any type of photoacoustic measurement, so a chamber containing a sample for analysis must be well insulated from outside noise and vibration. The photoacoustic effect due to surrounding materials such as the chamber itself must also be minimizedeven the chamber itself will demonstrate some amount of photoacoustic emission, and this effect must be taken into account by the experimenter. Modern photoacoustic experiments commonly employ chambers with cylindrical or spherical symmetry in order to take advantage of acoustical resonances. In this case, a standing wave is formed by tuning the applied laser to the resonance frequency of the chamber. This resonance amplifies the sound signal and allows it to be more easily detected.

This method of acoustic resonance has become so important in modern photoacoustics that a deeper mathematical discussion is warranted. The ideal model of a lossless gas in a rigid, perfectly insulated cylinder of length L and radius R0 leads to the following expression for resonance frequencies6:
1/ 2 2 2, ) c +# " mn & # n z & . = % ( +% ( 2 +$ R0 ' $ L ' . * -

f nmn z

where n, m, and nz are the eigenvalues of the radial, azimuthal, and longitudinal modes, respectively, and! nm is obtained from the mth Bessel function. [Fig. 4] "

Figure 4 Resonant modes in a cylinder of length L and radius R0 (From Hess) The acoustic Q-factor, a measure of the quality of the resonance, determines how much the acoustic signal is amplified. Enhancements of up to 1000 can be achieved with a cylindrical chamber, and up to 10000 with a spherical chamber. Resonant photoacoustic spectrometry relies on extensive computer control to tune to the resonant modes, and it is one of the most reliable methods currently available for the measurement of most thermophysical and kinetic properties of a gas. Concentrations of gases have been measured with photoacoustics to levels of parts per trillion, making it an indispensable tool in pollution monitoring and other trace

gas detection.7 When compared to conventional gas analysis methods, photoacoustic spectroscopy affords high sensitivity with an uncomplicated setup that lends itself well to portability. Another factor contributing to the proliferation of photoacoustics across a broad range of applications is the recent development of low-cost components. As the cost of assembling a photoacoustic instrument has decreased, photoacoustic spectroscopy has become a much more viable tool for industrial and other non-research based applications. The extensive history of the photoacoustic effect, from its almost accidental discovery to its eventual place in modern spectroscopy, is unique among the pantheon of physics phenomena. Bell and his colleagues were able to envision the practical applications of the effect, but lacked the technology to realize them. The precision afforded by modern optical equipment has been able to completely revive an idea that was truly ahead of its time, and will continue to improve upon it well into the future.

Lscher, Edgar. Photoacoustic Effect in Condensed MatterHistorical Development in Lscher, Edgar, et al., eds. Photoacoustic Effect: Principles and Applications. Braunschweig: Friedr. Vieweg & Sohn, 1984. p. 1. 2 Production of Sound by Radiant Energy The Manufacturer and Builder. Vol. 13, Issue 7. New York: Western & Co. July, 1881. p. 156. 3 Hess, P. and Fiedler, M. Laser Excitation of Acoustic Modes in Cylindrical and Spherical Resonators: Theory and Applications in Hess, Peter, ed. Topics in Current Physics: Photoacoustic, Photothermal and Photochemical Processes in Gases. Berlin Heidelberg: Springer-Verlag, 1989. p. 85. 4 Rosencwaig, Allan. Photoacoustics and Photoacoustic Spectroscopy. New York: John Wiley & Sons, 1980. p. 12. 5 Lscher, Edgar. Photoacoustic Effect in Condensed MatterHistorical Development in Lscher, Edgar, et al., eds. p. 10. 6 Hess, P. and Fiedler, M. Laser Excitation of Acoustic Modes in Cylindrical and Spherical Resonators: Theory and Applications in Hess, Peter, ed. p. 89. 7 Sigrist, M. W., et al. Atmospheric and Exhaust Air Monitoring by Laser Photoacoustic Spectroscopy in Hess, Peter, ed. p. 173.