Theory Photoacoustics
Theory Photoacoustics
Theory Photoacoustics
adiabatic coefficient, the heat expansion coefficient, this wave cannot propagate far away from the heat-
the thermal diffusivity and heat capacity at constant ed region; it appears only in the neighbourhood of
volume, the density of the deposited heat power, the the exciting light beam. In the sound wave a quasi-
isothermal compressibility and the dynamic viscosity, adiabatic state change propagates with the velocity
respectively. For solid materials the NavierStokes of sound; here the orders of magnitude of the relative
equation is replaced by the wave equation of the changes in pressure, temperature and density are the
longitudinal elastic waves. same. The amplitude of the periodic pressure change
The heat power density H, released in the material is proportional to the time-varying (AC) component
as the result of all nonradiative de-excitation process- of the released heat power density and inversely pro-
es, appears as the source term on the right hand side portional to the modulation frequency.
of the heat-diffusion equation. The spatial size and As the average of the intensity of a modulated
shape of the source volume depend on the light-beam light beam is nonzero, the heat energy in the illumi-
geometry and on the absorption length in the materi- nated volume will rise continuously. Therefore, the
al. Similarly, the time dependence of the heat source temperature will slowly increase and the density will
is determined by the time evolution of the light exci- decrease until the heat deposition rate is equal to the
tation and by the relaxation processes in the material. loss rate due to heat conduction. This process is also
A photoacoustic effect can be generated by modulat- governed by the heat-diffusion equation. For a
ed radiation as well as by pulsed radiation. As the closed cell the average density is constant; therefore
theoretical treatments of the two cases are different, a pressure rise will occur. This DC component of the
they will be discussed separately. released heat power density changes the thermody-
namic state of the material, in particular in very
Modulated PAS small PA detectors ( cm3).
In this case the intensity (or the wavelength) of the The amplitude of the periodic temperature change
incident light beam is modulated by an angular (T) is also proportional to the AC component of the
frequency Z to generate the acoustic signal. As the heat power density and inversely proportional to the
modulation frequency is usually in the audio modulation frequency. This means that the PA and
frequency range, the time delay between heat release PT effects are inherently coupled; the heat deposited
and light intensity may be negligible. In this case the by the interaction of radiation with the material gen-
source term has the same time dependence as the erates a localized temperature rise, a thermal wave
light intensity. Assuming an exp(i(Ztkr)) depend- and a propagating sound wave. The first two effects
ence of the variables, T, p and u, two independent will result in a periodically pulsating temperature
plane wave solutions of Equations [1] and [3] can be distribution.
derived: a thermal wave and a sound wave. The
wave-lengths of the two plane waves can be deter- Pulsed PAS
mined from the corresponding eigenvalues of the
wave vector k, taking into account that the length In the case of pulsed excitation, the absorption of
k = k of the wave vector (called wavenumber) is photons ceases when the laser pulse is over, but the
inversely proportional to the wavelength O (k = 2/O). relaxation processes will continue until the full ther-
The eigenvalues of the wavenumber for the thermal malization of the absorbed energy is achieved.
and sound wave may be given as k2th iZ/NP and Therefore, the duration of the thermal pulse is al-
k2s Z2/c2(1 iZQ/c2), respectively, where NP, Q = 4 K/ ways longer than that of the light pulse. Neverthe-
3 U and c are thermal diffusivity at constant pressure, less, the heat pulse may be regarded as instantaneous
the effective kinematic viscosity and the sound veloc- acoustic excitation if the characteristic time of the
ity, respectively. As the orders of magnitude of NP acoustic event is much larger than the duration of
and c are 105107 m2 s1 and 102104 m s 1 respec- the heat pulse. Two quantities characterize the
tively, the wavelength of the thermal wave is much acoustic process, namely the transit time Ws of the
shorter than that of the sound wave. That is, two sound through the heated volume and the response
types of waves are simultaneously generated: a very time of the PA detector. The value of Ws is usually in
strongly damped thermal wave with submillimetre the microsecond range (Figure 2), because the laser
wavelength, and a slightly damped sound wave with beam diameter usually does not exceed a few milli-
wavelengths in the centimetre to metre range. The metres in PAS. The PA response time depends on the
thermal wave corresponds more or less to an isobar- period of the eigenmodes of the detector and is usu-
ic thermal expansion, i.e. the changes of the temper- ally in the millisecond range (Figure 2). As the pulse
ature and density are much larger than that of the duration of most pulsed lasers is in the nanosecond
pressure. Because of the large damping coefficient, range, and in many cases, such as V-V and V-T
1818 PHOTOACOUSTIC SPECTROSCOPY, THEORY
Figure 3 Modelling of the gas temperature distribution as a PA detectors excited by modulated light
function of the radial distance from the light excitation source.
The diameter of the light beam was 6 mm and the pulse duration A simple PA detector consists of a cavity and a micro-
20 ns. The three curves represent three different time delays phone to monitor the acoustic signal (Figure 4A).
after illumination. Even such a simple system has acoustic resonances. If
the modulation frequency is much smaller than the
relaxation in gases, the relaxation time is also in the lowest resonance, the PA detector or PA cell operates
nanosecond to microsecond range, the source term in a nonresonant mode. Such a PA cell is frequently
of Equation [1] may be regarded as a Dirac-delta called a nonresonant cell in the literature. In this
pulse. The governing equations (Eqns [1] to [3]) can case the sound wavelength is much larger than the
be solved by the Greens function technique, taking cell dimensions and thus the sound cannot propa-
into account the Greens functions of both the gate. The average pressure in the detector will oscil-
thermal and acoustic problems. The solution is late with the modulation frequency. The amplitude
composed of a slowly broadening quasi-Gaussian of the oscillation may be determined by integrating
temperature distribution and an outward propagat- Equations [1] to [3] over the volume of the detector.
ing sound pulse of duration 2 Ws. After a short time The pressure amplitude will be inversely proportion-
the sound pulse will be separated from the thermal al to the volume of the cell. The photoacoustically
distribution, allowing the measurement of both fea- generated pressure can be approximated by the
tures separately (Figure 3). The spatial symmetry of expression
the solution depends on the shape and size of the
heated region. In strong absorbers, the heated region
is usually small compared to the sound wavelength;
therefore mostly spherical sound waves are pro-
duced. In weakly absorbing gases, cylindrical acous-
tic waves are generated. The outward-propagating where D, l, WL, Z, Vcell and J denote the absorption
primary wavefront can be detected by appropriate coefficient of the material at the light pass length, the
high-frequency pressure sensors. As the achievable incident light power, the modulation frequency, the
sensitivity and signal-to-noise (S/N) ratio are small, cell volume and the adiabatic coefficient of the mate-
the direct detection of the primary waves has no rial, respectively. In the case of a small cell and low
practical significance. In practice the acoustic excita- modulation frequency, the signal may be quite large.
tion takes place inside a PA detector, and the time The PA signal has a 90 phase lag with respect to the
evolution of the acoustic signal is strongly influenced light intensity. Unfortunately, the noise also increases
by the properties of this detector. with decreasing frequency and volume; thus the S/N
ratio will usually decrease.
Determination of the PA signal in a As mentioned, the acoustic and thermal processes
are inherently coupled. Until the cell dimensions are
PA detector much larger than the size of the pulsating thermal dis-
The actual solutions of the governing equations tribution, the simple model described above can be
(Eqns [1] to [3]) depend on the boundary conditions applied. The thermal wave is usually not completely
PHOTOACOUSTIC SPECTROSCOPY, THEORY 1819
damped at the walls of the cell in the case of a very where c, R and L are the sound velocity of the gas in
small cell and very low modulation frequency. Then the cavity, the radius and the length of the cylinder,
both the average temperature and the amplitude of respectively. The indices m, n and nz may take the
the temperature oscillation will be influenced by the values 0, 1, 2, etc. The quantity m,n is the nth zero of
heat conduction through the cell walls to the environ- the derivative of the mth-order Bessel function divid-
ment. As in a closed cell the pressure is proportional ed by .
to the temperature, the PA signal will also depend on When only one index is nonzero, the eigenmodes
the heat conduction through the walls. Since the the- separate into longitudinal (nz 0), radial (n 0) and
oretical modelling of this effect is practically impossi- azimuthal (m 0) modes (Figure 5). In the other
ble, such small cells and very low modulation mixed eigenmodes the spatial distribution of the
frequencies allow only a qualitative signal analysis. sound pressure is much more complicated.
A special case should be mentioned here, one of The modulation frequency may be tuned to one of
the oldest arrangements among PA detectors. the eigenresonances of the PA detector. Such reso-
Termed the gas-microphone cell it is used for inves- nant PA cells or detectors have found widespread
tigating samples of condensed materials (Figure 4B). application in PA trace gas measurements. Since the
It usually consists of a small cylinder equipped with eigenmodes of a lossless cavity are orthogonal, the
a sample holder, a microphone and a window. The sound pressure field in a lossy cavity can be approxi-
gas in the cell is nonabsorbing; only the sample and mated in the form of a series expansion of the eigen-
the backing material (in the case of an optically thin modes, where the amplitudes of the terms depend on
sample) absorb the incident radiation. The PA signal frequency. In fact, each amplitude function is a reso-
is produced in an indirect way; the thermal waves nance curve characterized by the corresponding reso-
generated in the solid sample are transmitted to the nance frequency and quality factor (Q factor). The
gas, and the periodic heat expansion of the gas above first term of the series expansion determines the
the sample surface acts as a piston and produces sound pressure below the lowest resonance. To aid
pressure oscillations in the closed cell volume. As the understanding of the behaviour of a resonant PA cell
penetration depth of the thermal wave is usually a computer simulation is shown in Figure 6, for
much smaller than the diameter of the light beam, which the frequency dependence of the PA signal at
one-dimensional theoretical modelling is possible. one end of a closed cylinder filled with a strongly ab-
In resonant photacoustics, an acoustic resonator sorbing gas was calculated. It can be seen that sever-
with an optimized geometry such as a cylinder or al resonances (the odd-numbered longitudinal ones)
sphere is used as the gas cell. Such an acoustic system lie on a nonresonant curve. For well-separated sharp
has several eigenresonances, whose frequencies de- resonances, only two terms of the series expansion
pend on the geometry and size of the cavity. For a are necessary to determine the sound pressure
lossless cylinder, the resonance frequencies of the around a certain resonance. These are the first non-
different eigenmodes can be calculated from the resonant term, which is independent of the spatial
equation coordinates but depends inversely on the frequency,
and the resonant term, corresponding to the selected
eigenmode. This term depends on the overlap of the
acoustic mode pattern and the light beam distribu-
tion, on the position of the microphone and on the
Figure 4 PA setups for monitoring the PA signal with a microphone in a resonator: (A) gas or liquid, (B) solid sample in a gas
microphone cell.
1820 PHOTOACOUSTIC SPECTROSCOPY, THEORY
Figure 5 Schematic representation of the longitudinal, azimuthal and radial acoustic modes in a cylindrical resonator.
quality factor of the eigenresonance. In the case of properly tuned to the selected acoustic resonance
high Q factors (Q > 100), the contribution of the (acoustic amplifier).
nonresonant term can be neglected and the PA signal If the modulation frequency is so low that the cor-
amplitude at the resonance frequency Zj and at the responding wavelength is much longer than the
position rM of the microphone can be calculated as dimensions of the detector, Equation [3] may be used
to calculate the PA signal. Nonresonant operation is
also possible by tuning the modulation frequency
away from a resonance. In such cases the PA signal
can be estimated by substituting Q = 1 into Equation
[6], but a better accuracy may be achieved by taking
into account the nonresonant term and at least the
where l, pj, Uj, Qj, Dj, Vcell, D and WL are the length neighbouring eigenmodes in the series expansion.
of the light path within the cell, the pressure distribu-
tion of the jth eigenmode of the cell, the overlap inte-
gral of the light intensity distribution with pj, the Q
factor and the normalization factor of the jth eigen-
mode, the cell volume, the absorption coefficient and
the incident light power, respectively. As the quanti-
ties in the first term of Equation [6] are independent
of the light power and the absorption coefficient, the
first term may be regarded as a characteristic setup
quantity, called the cell constant, of the PA ar-
rangement.
Since the resonance frequency depends on the
speed of sound, a temperature drift of the gas inside
the cavity causes a shift of all resonance frequencies.
In modulated PAS this problem can be solved by tem-
perature stabilization, by continuous monitoring of
the gas temperature or by synchronizing the modula-
tion frequency to the resonance peak using appropri-
ate electronics.
As the modulation frequency of a CW light source
may be arbitrary, a given PA detector can operate in
both the nonresonant and resonant modes. The main
Figure 6 Modelling of the frequency-dependent PA signal. The
advantage of resonant operation is the amplification excited modes are the first (001), third (003) and fifth (005)
of the PA signal by the Q factor of the resonator if longitudinal modes of the cavity. The dotted line shows the
the modulation frequency of the incoming light is nonresonant contribution.
PHOTOACOUSTIC SPECTROSCOPY, THEORY 1821
the linear dependence of the PA signal on the pulse Photoacoustic, Photothermal and Photochemical
energy must always be checked in pulsed PAS. Processes in Gases, pp 125170, Vol 46 in Topics in
Current Physics. Berlin: Springer.
Fiedler M and Hess P (1989) Laser excitation of acoustic
List of symbols modes in cylindrical and spherical resonators: theory
c = sound velocity; CV = heat capacity at constant and applications. In: Hess P (ed) Photoacoustic, Photo-
volume; Dj = normalization factor of jth eigenmode; thermal and Photochemical Processes in Gases , pp 85
EL = pulse energy; H = heat power density; k = |k|; 121, Vol 46 in Topics in Current Physics. Berlin:
k = wave vector; KT = isothermal compressibility; Springer.
Hess P (1992) Principles of photoacoustic and photother-
L = cavity length; l = light path length; P = pressure;
mal detection in gases. In: Mandelis A (ed) Progress in
p = PP0; Qj = Q factor of jth eigenmode; r = position
Photothermal and Photoacoustic Science and Technol-
vector; R = cavity radius; T = temperature; ogy, Vol 1, pp 153204. New York: Elsevier.
U = overlap integral; u, v = particle velocity vector; Morse PM and Ingard KU (1986) Theoretical Acoustics.
WL = incident light power; D = absorption coefficient; Princeton, NJ: Princeton University Press.
E = thermal expansion coefficient; J = adiabatic coef- Pao YH (1977) Optoacoustic Spectroscopy and Detection.
ficient; K = dynamic viscosity; T = T T0; NV, NP = New York: Academic Press.
thermal diffusivity at constant volume, pressure; Rosencwaig A (1980) Photoacoustics and Photoacoustic
O = wavelength; Q = effective kinematic viscosity = 4 K/ Spectrosopy. New York: Wiley.
3 U; U = density; Ws = transit time of sound; Fm,n = the Schfer S, Mikls A and Hess P (1997) Pulsed laser reso-
nth zero of the derivative of the mth-order Bessel nant photoacoustics/applications to trace gas analysis.
In: Mandelis A and Hess P (eds) Progress in Photother-
function (1/); Z = angular frequency of modula-
mal and Photoacoustic Science and Technology , Vol 3,
tion.
pp 254289. Bellingham, WA: SPIE.
See also: Laser Spectroscopy Theory; Light Sources Schfer S, Mikls A and Hess P (1997) Quantitative signal
and Optics; Photoacoustic Spectroscopy, Applica- analysis in pulsed resonant photoacoustics. Applied
tions. Optics 36: 32023211.
West GA, Barrett JJ, Siebert DR and Reddy KV (1983)
Photoacoustic spectroscopy. Review of Scientific
Further reading Instruments 54: 797817.
Diebold GJ (1989) Application of the photoacoustic effect Zharov VP and Letokhov VS (1986) Laser Optoacoustic
to studies of gas phase chemical kinetics. In: Hess P (ed) Spectroscopy. Berlin: Springer.
Photoelectron Spectrometers
Lszl Szepes and Gyrgy Tarczay,
HIGH ENERGY
Etvs University, Budapest, Hungary
SPECTROSCOPY
Copyright 1999 Academic Press Methods & Instrumentation