Photoacoustic Spectroscopy, Methods and Instrumentation☆

MW Sigrist, ETH Zürich, Zurich, Switzerland

ã 2017 Elsevier Ltd. All rights reserved.

Introduction The properties of piezoelectric transducers and microphones

as pressure sensors are discussed below.
Since the discovery of the photoacoustic (PA) effect by Bell in If the use of pressure sensors is not appropriate, because,
1880 who used the Sun as radiation source, a foot-operated e.g., a piezoelectric transducer cannot be attached to the sam-
chopper for modulation and an earphone as acoustic detector, ple or measurements need to be done at high temperatures
the PA effect has found numerous applications as a sensitive which hinders the application of microphones, noncontact
and rather simple technique for determining optical, thermal techniques are to be applied. As shown in Figure 1(c) the
and mechanical properties of all kinds of samples. This article induced spatial and temporal gradient of the refractive index
focuses on methods and instrumentation employed in spectro- can be sensed in this case by monitoring the deflection of a
scopic applications. Since photothermal spectroscopy is dis-
cussed in another section, those schemes are only briefly
mentioned here whereas emphasis is put on instrumentation
used in photoacoustic spectroscopy.
The spectroscopic applications of the PA effect are not dis-
cussed here but only the technique itself, its characteristics and
implementation. Although the PA method has been around for
more than a century it is particularly the advent of lasers as
radiation sources with high spectral brightness that has initi-
ated a renaissance of the PA effect. In the meantime a great
variety of experimental schemes have been developed and
render the PA method a very versatile spectroscopic tool.

Photoacoustic and Photothermal Schemes

Experimental Arrangements
As the photoacoustic (and related photothermal (PT)) phe-
nomena comprise a large diversity of facets there exist various
detection techniques which rely on the acoustic or thermal
disturbances caused by the absorbed radiation. The selection
of the most appropriate scheme for a given application
depends on the sample, the sensitivity and specificity to be
achieved, ease of operation, ruggedness, and any requirement
for non-contact detection, e.g. in aggressive media or at high
temperatures and/or pressures. Figures 1–3 present the most
typical arrangements applied for solid, liquid and gaseous
samples, respectively.
Experimental schemes for PA studies on solid samples
include the measurement of the generated pressure wave either
directly in the sample with a piezoelectric sensor for the pulsed
regime, or indirectly in the gas which is in contact with the
sample by a microphone. These most widely used setups are
depicted in Figure 1(a) and 1(b). The indirect detection of the
Figure 1 Typical experimental arrangements used for photoacoustic
generated acoustic wave in the gas phase with the microphone
(PA) and photothermal (PT) studies on solids. As indicated one
is inevitable if a direct contact with the sample is not readily differentiates between modulated or pulsed incident radiation.
possible, e.g. for samples such as powders, gels or grease. (a) Indirect PA detection by microphone in the gas phase. (b) Direct
PA detection with PZT transducer or PVDF foil attached to solid. (c) PT
☆
Change History: August 2014. MW Sigrist updated the text further sensing of the gradient of the refractive index with probe beam deflection
readings to this entire article. in the (transparent) sample (probe beam 1), or above the sample surface
Markus W. Sigrist, Photoacoustic Spectroscopy, Methods and (Mirage effect, probe beam 2). Monitoring of the generated surface
Instrumentation, In Encyclopedia of Spectroscopy and displacement (probe beam 3) or of the change of surface reflectivity
Spectrometry (Second Edition), edited by John C. Lindon, (probe beam 4). (d) PT radiometry senses the induced change of the
Academic Press, Oxford, 1999, Pages 2146-2150. IR radiation that is radiated off the sample surface.

598 Encyclopedia of Spectroscopy and Spectrometry, Third Edition http://dx.doi.org/10.1016/B978-0-12-409547-2.11308-3

 Photoacoustic Spectroscopy, Methods and Instrumentation 599

probe beam either within the (transparent) sample or directly generated acoustic waves are detected by a piezoelectric trans-
above the (plane) sample surface (PT beam deflection or ducer with fast response time. Usually just the first peak of the
so-called mirage effect). Changes of the surface reflectivity or ringing acoustic signal is taken and further processed. Pulse-to-
slight deformations of the surface (PT beam displacement) can pulse variations of the laser power are accounted for by nor-
also be detected in a non-contact manner by a probe beam. malizing the piezoelectric signal with the laser power measured
Finally, as depicted in Figure 1(d), variations of the thermal with the power meter after the cell.
radiation from the surface can be monitored with an infrared Another area of interest is the measurement of opaque or
detector (PT radiometry). This method is of particular interest strongly absorbing liquids. A simple open PA cell called an
for measurements at elevated temperatures owing to the optothermal window was developed for this purpose as dis-
increased radiation intensity according to Stefan–Boltzman’s played in Figure 2(b). It essentially consists of an uncoated
law. Still other techniques include pyroelectric detection in ZnSe window to which an annular lead zirconate titanate
thin films, thermal lensing and interferometric methods. (PZT) piezotransducer is glued from the bottom. The excita-
The typical experimental arrangement for absorption spec- tion beam from a laser passes unobstructedly through this
troscopy in weakly absorbing liquids is shown schematically in window and is absorbed by a droplet of the sample deposited
Figure 2(a). The beam of a pulsed tunable laser is directed on the other side of the ZnSe disc. The generated heat diffuses
through the PA cell that contains the sample under study. The into the disk which expands. The induced stress is then
recorded by the PZT transducer. Unlike in conventional trans-
mission spectroscopy where the cell thickness is the restricting
factor in dealing with strongly absorbing samples, the magni-
tude of the optothermal window signal depends solely on the
product between the absorption coefficient and the thermal
diffusion length whereby the latter can be adapted via the
modulation frequency.
The typical setup for gas phase measurements is shown in
Figure 3(a). A tunable laser with narrow linewidth or a con-
ventional (broadband) radiation source followed by optical
filters is used. In general, amplitude-modulated (or sometimes
pulsed) or wavelength-modulated (WM) radiation is directed
through the PA cell. The acoustic sensor is usually a commer-
cial electret microphone or a condenser microphone. These
devices are easy to use and sensitive enough for trace gas
studies with very low absorptions. Often, the detection thresh-
old is neither determined by the microphone responsivity Rmic
itself nor by the electrical noise but rather by other sources
(absorption by desorbing molecules from the cell walls, win-
Figure 2 Typical experimental arrangements used for PA detection in dow heating, ambient noise, etc.). However, if this latter back-
liquids. (a) PZT detection of aoustic wave generated by pulsed radiation ground is known from reference measurements, the ultimate
in weakly absorbing liquid. (b) Optothermal window setup applied for detection sensitivity is determined solely by fluctuations of the
studies on strongly or opaque liquids with modulated or pulsed radiation. radiation intensity, and by microphone and amplifier noise.

Figure 3 Typical experimental PA and PT arrangements used for gas monitoring with tunable laser sources. (a) PA detection with conventional
microphone in resonant gas cell for modulated cw radiation or in non-resonant cell for pulsed radiation. (b) Noncontact refractive index sensing
schemes with displaced collinear or transverse probe beam (PA deflection, 1), thermal lensing (2), or collinear probe beam (PT deflection, 3).
600 Photoacoustic Spectroscopy, Methods and Instrumentation

The frequency dependence of Rmic is usually rather small and and appropriate filters to avoid absorption interferences with
the temperature dependence may have to be taken into other species are used as compact gas sensors, e.g. for indoor
account in special cases only. If modulated radiation is CO2 monitoring.
employed the microphone signal is fed to a lock-in amplifier However, since the generated PA signal is proportional to
locked to the modulation frequency. Since according to theo- the absorbed (and thus to the incident) radiation power, pow-
retical considerations the microphone signal amplitude is pro- erful radiation sources, particularly lasers offering high spectral
portional to the absorbed power for weakly absorbing media, brightness, are advantageous for achieving high detection sen-
the average radiation power is recorded simultaneously by a sitivity and selectivity in spectroscopic applications. In the UV
power meter for normalization. In more recent times, new and visible spectral range, excimer and dye lasers have been
schemes have been introduced, in particular quartz-enhanced employed whereas in the mid-infrared (fundamental or mid-
photoacoustic spectroscopy (QEPAS) and cantilever-enhanced IR) wavelength range line-tunable CO2 and CO lasers have
photoacoustic spectroscopy (CEPAS). dominated the applications for long times. Near infrared
If pulsed radiation is employed the microphone bandwidth diode lasers with sufficient power for PAS are often used for
is often not sufficient to resolve the temporal shape of the monitoring overtones and combination bands of molecular
generated acoustic pulses. However, common microphones fundamental absorptions. Widely tunable narrowband all-
can still be used even for nanosecond laser pulses because the solid-state laser devices in the mid-IR region for accessing the
length of a single acoustic pulse is essentially determined by (much stronger) fundamental absorptions include optical
the transit time of the acoustic wave across the beam radius. parametric oscillators (OPO’s) and difference frequency gener-
Normalized PA amplitudes are obtained by dividing the micro- ation (DFG) in nonlinear crystals. Furthermore, near- to mid-
phone signal peaks by the corresponding laser pulse energy infrared interband cascade lasers (ICLs) and mid-infrared tun-
that is recorded by a sensor such as a pyroelectric detector. able quantum cascade lasers (QCLs, often with external cavity)
Averaging over several pulses improves the signal-to-noise represent very interesting sources for compact sensing devices.
ratio. Another approach for pulsed radiation consists of using Most recent and ongoing developments of tunable mid-
an acoustic resonator with high Q-factor as gas cell, recording infrared lasers such as diode-pumped lead salt vertical
the microphone signals in the time domain but analyzing the extended cavity surface emitting lasers (VECSELs), continue
PA signal amplitudes after Fourier transformation in the fre- to change the situation.
quency domain. The excited cell resonances then appear in the
PA frequency spectra.
An important issue for many applications concerns the
Modulation Schemes
calibration of the entire PA or PT detection system. Since the
PA signal depends on many factors that are not known with Modulation schemes can be separated into the modulation of
sufficient accuracy, a straigthforward calibration is often the incident radiation and the modulation of the sample
achieved by employing a reference sample with known absorp- absorption itself. The first technique includes the most widely
tion. As example, certified gas mixtures (trace gas diluted in a used amplitude modulation (AM) of continuous radiation by
nonabsorbing buffer gas) or well characterized dye solutions in mechanical choppers, electro-optic or acousto-optic modula-
the case of liquids are used. The situation is more difficult with tors as well as the modulation of the source emission itself by
solid and biological samples, particularly layered media, pow- current modulation or pulsed excitation. In comparison to AM,
ders, gels or tissue. In such cases, quantitative data are difficult, frequency- (FM) or wavelength- (WM) modulation of the radi-
if not impossible, to obtain. But even qualitative instead of ation may improve the detection sensitivity by eliminating the
quantitative spectra are often valuable especially when other continuum background caused by a wavelength-independent
spectroscopic techniques fail owing to opaqueness or strong absorption, e.g., of the cell windows, known as window heat-
scattering of the sample. ing. This type of modulation is obviously most effective for
It should be emphasized that numerous different versions absorbers with narrow linewidth and most easily performed
and modifications of these general schemes have been pre- with radiation sources whose wavelength can rapidly be tuned
sented in the literature such as QEPAS and CEPAS mentioned within a few wavenumbers. Pulsed excitation is often applied
above. Furthermore, combinations of conventional methods, for liquids but is also of interest for gaseous samples because it
such as Fourier-transform IR (FTIR) or gas-chromatography permits time gating and the excitation of acoustic resonances.
(GC), with PA detection have been reported. Some types of In certain cases the modulation of the absorption charac-
PA detection schemes are also implemented in commercial teristics of the sample itself is advantageous. In gas studies the
spectrometers. Stark or Zeeman effect has been employed, i.e., by applying a
In the following the different components of PA spectrom- modulated electric or magnetic field to the sample. The result is
eters are briefly discussed. a suppression of the continuum background and an enhance-
ment of detection selectivity in multicomponent samples
because, e.g., Stark modulation only affects molecules with a
Radiation Sources
permanent electric dipole moment like ammonia (NH3) or
In commercial PA spectrometers, incoherent sources such as nitric oxide (NO) while other, possibly interfering molecules
incandescent lamps are employed in combination with filters are not affected. Finally, combinations of both amplitude and
or with an interferometer, or also light-emitting diodes (LEDs). sample absorption modulation have been successfully applied,
Devices equipped with a small light bulb with either a chopper e.g., for the sensitive detection of ammonia in the presence of
or direct current modulation as modulated radiation source absorbing water vapor and carbon monoxide.
 Photoacoustic Spectroscopy, Methods and Instrumentation 601

The scheme of QEPAS is based on the modulation of the For studies in the gas phase, commercial microphones are
source whose beam is guided through the gap between the employed. These include miniature electret microphones such
prongs of a quartz tuning fork (QTF), filled with the sampling as Knowles or Sennheiser models with typical responsivities
gas. The prongs are bent in opposite directions by the gener- Rmic of 10–20 mV Pa 1 as well as condenser microphones, e.g.
ated acoustic wave resulting in a piezoelectric signal which is Brüel and Kjær models with typical Rmic of 100 mV Pa 1. Usu-
normally recorded at the resonance frequency of typically ally Rmic depends only weakly on frequency. The electret micro-
32 kHz. phones produced for hearing aids exhibit a rather flat
frequency response between, say, 20 Hz and 20 kHz whereas
the bandwith Dn of condenser microphones extends to fre-
Photoacoustic Cell Designs
quencies of 100 kHz. All these microphones are thus well
The PA cell serves as a container for the sample under study and suited for typical modulation frequencies in the 100 Hz to
for the microphone or some other device for the detection of kHz range. For pulsed applications, the general relation
the generated acoustic wave. An optimum design of the PA cell between Rmic and Dn, as well as the occurrence of external
represents a crucial point when background noise ultimately noise implies a reduction of the signal-to-noise ratio for very
limits the detection sensitivity. In particular for trace gas appli- large bandwidths so that miniature electret microphones are
cations, many cell configurations have been presented includ- often appropriate detectors also in this case. The detection
ing acoustically resonant and nonresonant cells, single- and sensitivity can be enhanced by adding the signals of several
multipass cells, as well as cells placed intracavity. Nonresonant microphones. In such a configuration the signal increases with
cells of small volume are mostly employed for solid samples the number of microphones used whereas the microphone
with modulated excitation or for liquids and gaseous samples random noise only increases with the square root of their
with pulsed laser excitation. As unique example, we have devel- number. Since electret microphones are small and cheap, a
oped at our laboratory a small-volume cell equipped with a number of them can be arranged in a still compact geometry.
“tubular” acoustic sensor consisting of up to 80 single minia- A further improvement of sensitivity is expected from the
ture microphones. These microphones are arranged in eight insertion of an electrical filter that cuts the low-frequency
linear rows with ten microphones in each row. The rows are components below, say, 1 kHz of the signal because these
mounted in a cylindrical geometry parallel to the exciting laser components contribute less to the increase of the signal-to-
beam axis and located on a circumference around the axis. This noise ratio than the higher-frequency components. Finally,
configuration is thus ideally adapted to the geometry of the an adaption of the frequency response of the microphone
generated acoustic waves. pre- and amplifier stages to that of the microphone is advan-
Resonant cells in combination with modulated excitation tageous to fully exploit all the sensed frequency contributions
are normally applied for gas monitoring. These cells are oper- except noise components at frequencies not contributing to the
ated on longitudinal, azimuthal, radial, or Helmholtz reso- acquired signal.
nances. The signal enhancement by the Q-factor (usually While the QEPAS scheme uses the tuning fork as sensing
>100) is often advantageous. Resonance frequencies lie in device, the CEPAS method relies on a cantilever whose bending
the kHz range resulting in resonance widths of a few Hz. by the acoustic wave generated in the cell is recorded with a
Furthermore, the gas handling for the cell can be designed in diode laser-based interferometer.
such a way that the gas in- and outlets are located at pressure If there is a need for noncontact detection, refractive index
nodes of the acoustic resonance which allows measurements in sensing, notably thermal lensing and both PA and PT deflec-
flowing gas with flow rates on the order of 1 l min 1 without tion, are employed. These methods use a pump beam and a
increasing the noise level. probe beam (HeNe or diode laser) in either collinear or trans-
Finally, cells developed for special purposes have been verse arrangement as shown in Figure 3(b). In comparison to
suggested like windowless cells equipped with acoustic baffles the conventional PA method with pressure sensors, these
to reduce the influence of the ambient noise or heatable cells schemes offer similar sensitivity but require a somewhat more
for studying liquid samples with low volatility. sophisticated setup and imply a more difficult calibration.
Quartz-enhanced photoacoustic spectroscopy (QEPAS) can
be operated in the open air without cell although resonant
microtubes are often added for improved performance. See also: Laser Induced Optoacoustic Spectroscopy; Photoacoustic
Cantilever-enhanced photoacoustic spectroscopy (CEPAS) Spectroscopy, Applications; Photoacoustic Spectroscopy, Theory.
generally uses a longitudinal cell.

Detection Sensors
As mentioned above the acoustic disturbances generated in the Further Reading
sample are detected by some kind of pressure sensors. In Almond DP and Patel PM (1996) Photothermal Science and Techniques. London:
contact with liquid or solid samples these are piezoelectric Chapman & Hall.
devices such as lead zirconate titanate (PZT), LiNbO3 or quartz Mandelis A (ed.) (1992) Principles and Perspectives of Photothermal and
crystals with a typical responsivity R in the range of up to Volts/ Photoacoustic Phenomena. In: Progress in Photothermal and Photoacoustic
Science and Technology, vol. 1. New York: Elsevier.
bar or thin polyvinilydene-difluoride (PVF2 or PVDF)-foils Meyer PL and Sigrist MW (1990) Rev. Sci. Instrum. 61: 1779.
with lower responsivity R. These sensors offer fast response Pao Y-H (ed.) (1977) Optoacoustic Spectroscopy and Detection. New York: Academic
times and are thus ideally adapted for pulsed photoacoustics. Press.
602 Photoacoustic Spectroscopy, Methods and Instrumentation

Rosencwaig A (1980) Photoacoustics and Photoacoustic Spectroscopy. Chemical Tam AC (1986) Rev. Mod. Phys. 58: 381.
Analysis Series, vol. 57. New York: Wiley. Zharov VP and Letokhov VS (1986) Laser Optoacoustic Spectroscopy. Springer Series
Sigrist MW (1986) J. Appl. Phys. 60: R83. in Optical Sciences, vol. 37. Berlin: Springer.
Sigrist MW (1994) In: Sigrist MW (ed.) Air Monitoring by Spectroscopic Techniques. Kosterev AA, Tittel FK, Serebryakov DV, Malinovski AL, and Morozov IV (2005) Rev.
Chemical Analysis Series, vol. 127. New York: Wiley Chapter 4. Sci. Instrum. 76: 043105.
Tam AC (1983) In: Kliger DS (ed.) Ultrasensitive Laser Spectroscopy. New York: Kuusela T and Kauppinen J (2007) Appl. Spectr. Rev. 42: 443.
Academic Press.