SEMINAR REPORT ON

PHOTOACOUSTIC
SPECTROSCOPY

MOHAME
D NIJAS V
S9
I.S.P.

CUSAT

INTRODUCTION

Photo acoustic effect is a phenomenon which deals with the interaction of light (optics) and
sound (acoustics). The existence of an interaction between light and sound was discovered by
brillouin in the year 1922.
The photoacoustic effect or optoacoustic effect is the formation of sound waves following
light absorption in a material sample. In order to obtain this effect, the light intensity must
vary, either periodically (modulated light) or as a single flash (pulsed light).The
photoacoustic effect is quantified by measuring the formed sound (pressure changes) with
appropriate detectors, such as microphones or piezoelectric sensors. Most generally,
electromagnetic radiation of any kind can give rise to a photoacoustic effect. This includes
the whole range of electromagnetic frequencies, from gamma radiation and X-rays to
microwave and radio. Still, much of the reported research and applications, utilizing the
photoacoustic effect, is concerned with the near ultraviolet/visible and infrared spectral
regions. The time variation of the electric output (current or voltage) from these detectors is
the photoacoustic signal. These measurements are useful to determine certain properties of
the studied sample.

Physical mechanisms
Photothermal mechanism: Although much of the literature on the subject is concerned
with just one mechanism, there are actually several different mechanisms that produce the
photoacoustic effect. The primary universal mechanism is photothermal, based on the heating
effect of the light and the consequent expansion of the light-absorbing material. In detail, the
photothermal mechanism consists of the following stages:
(1) Conversion of the absorbed pulsed or modulated radiation into heat energy. (2) Temporal
changes of the temperatures at the loci where radiation is absorbed rising as radiation is
absorbed and falling when radiation stops and the system cools.(3) Expansion and contraction
following these temperature changes, which are "translated" to pressure changes.
The pressure changes, which occur in the region where light was absorbed, propagate within
the sample body and can be sensed by a sensor coupled directly to it. Commonly, for the case
of a condensed phase sample (liquid, solid), pressure changes are rather measured in the
surrounding gaseous phase (commonly air), formed there by the diffusion of the thermal
pulsations. The main physical picture, in this case, envisions the original temperature
pulsations as origins of propagating temperature waves ("thermal waves"), which travel in the
condensed phase, ultimately reaching the surrounding gaseous phase. The resulting
temperature pulsations in the gaseous phase are the prime cause of the pressure changes
there. The amplitude of the traveling thermal wave decreases strongly (exponentially) along
its propagation direction, but if its propagation distance in the condensed phase is not too
long, its amplitude near the gaseous phase is sufficient to create detectable pressure changes.
This property of the thermal wave confers unique features to the detection of light absorption
by the photoacoustic method

Other mechanisms: While the photothermal mechanism is universal, there could exist
additional other mechanisms, superimposed on the photothermal mechanism, which may
contribute significantly to the photoacoustic signal. These mechanisms are generally related
to photo physical processes and photochemical reactions following light absorption:
(1) Change in the material balance of the sample and/or the gaseous phase around the sample.

(2) Change in the molecular organization, which results in molecular volume changes.

Detection of the photoacoustic effect

In applying the photoacoustic effect there exist various modes of measurement. Gaseous
samples or condensed phase samples, where the pressure is measured in the surrounding
gaseous phase, are usually probed with a microphone. The useful applicable time-scale in this
case is in the millisecond to sub-second scale. Most often, in this case, the exciting light is
continuously chopped or modulated at a certain frequency (mostly in the range between ca.
1010000 Hz) and the modulated photoacoustic signal is analyzed with a lock-in amplifier
for its amplitude and phase, or for the inphase and quadrature components. When the pressure
is measured within the condensed phase of the probed specimen, one utilizes piezoelectric
sensors inserted into or coupled to the specimen itself. In this case the time scale is between
less than nanoseconds to many microseconds. The photoacoustic signal, obtained from the
various pressure sensors, depends on the physical properties of the system, the mechanism
that creates the photoacoustic signal, the light-absorbing material, the dynamics of the excited
state relaxation and the modulation frequency or the pulse profile of the radiation, as well as
the sensor properties.

PHOTOACOUSTIC SPECTROSCOPY
Photoacoustic spectroscopy is a sensitive technique for measuring small absorptions that is
mainly applies when minute concentrations of molecular species have to be detected in the
presence of other components at higher pressure. An example is the detection of spurious
pollutant gases in the atmosphere. Its basic principle may be summarized as follows:
The laser beam is sent through the absorber cell. If the laser is tuned to the
absorbing molecular transition Ei -> Ek, part of the molecules in the lower level Ei will be
exited into upper level Ek. by collisions with other atoms or molecules in the cell, these exited
molecules may transfer their excitation energy (Ei -Ek) completely or partly into translational,
rotational, or vibration energy of the collision partners. At thermal equilibrium, this energy is
randomly distributed onto all degrees of freedom, causing an increase of thermal energy and
with it a rise in temperature and pressure at a constant density in the cell.
When the laser beam is chopped at frequencies < 1/T, where T is the mean relaxation
time of the exited molecules, periodic pressure variations appear in the absorption cell, which
can be detected with a sensitive microphone placed inside the cell. The output signal S(volt)
of the microphone is proportional to the pressure change P induced by the absorbed
radiation power W. If saturation can be neglected, the absorbed energy per cycle is given by

W =N i ik ( 1k ) Pl t

Is proportional to the density Ni [cm-3] of the absorbing molecules in level li > , the
absorption cross sectionik , the absorption path length x, the cycle period t, and the
incident power PL. the signal decreases with increasing quantum efficiency k, unless the
fluorescence is absorbed inside the cell and contributes to the temperature rise.
A diagram is used to represent the phenomenon,

Since the absorbed energy W is transferred into kinetic or internal

energy of all N molecules per cm3 in the photoacoustic cell with the
volume V, the temperature rise T is obtained from,
W = fVNkT
Where f is the number of degrees of freedom that are accessible for each of the
N molecules at temperature T[k]. If the chopping frequency of the laser is
sufficiently high, the heat transfer to the walls of the cell during the pressure rise
time can be neglected. From the equation of state, we may obtain that
p = NkT = (2W)/fv
The output signal s from the microphone is then

Where the sensitivity Sm of the microphone not only depends on the

characteristics of the microphone but also on the geometry of photo-acoustic
cell.

Photoacoustic spectroscopy: gases

One advantage to photoacoustic spectroscopy is that it can be performed on all phases of
matter. When a species absorbs some of the incoming light, one of several mechanisms of deexcitation is intermolecular colliding, which ultimately leads to increases in translation
energy of the gas particles that is, heating. According to the various gas laws, an increase
in the temperature of the gas leads to an increase in the pressure of an isochoric (constantvolume) sample. If the incoming light is modulated modulation frequencies can vary from
single to several thousand hertz the gas pressure increases and decreases accordingly,
creating sound. Varying the wavelength of the incoming light will change the amount of light
absorbed, the amount of pressure changes occurring, and the amount of sound produced, and
a spectrum of loudness versus wavelength can be produced. One useful aspect of
photoacoustic spectroscopy of gases is that very bright light sources lasers can be used
to detect very tiny concentrations of a particular gas, on the order of parts per trillion. This
makes photoacoustic spectroscopy very useful in following the concentrations of trace gases
in mixtures, like soot in diesel exhaust or NOx in the atmosphere. Photoacoustic spectroscopy
can also be limited because laser light is not very broad in bandwidth; the analyte molecule
must absorb some light from the source in order to be detectable.

Photoacoustic Signal Linearization

The phase of the photoacoustic signal saturates at higher values of the absorption coefficient
as shown in the last figure and this allows calculation of a linearized spectrum that has a
linear dependence extending to higher values of the absorption coefficient. This reduces the
truncation of strong absorbance peaks which are troubling to classical spectroscopists but turn
out to actually have little influence when modern chemometrics are use in both quantitative
and qualitative analyses. Linearization, however, is very useful in reducing sampling depth

and increasing surface specificity as illustrated later in the case of a siloxane treated fabric.

With rapid scan FTIRs sampling depth, L, depends on the interferometers OPD mirror
velocity, v, the samples thermal diffusivity, D, and the wave number, , at a particular point
in a spectrum. L is defined as the reciprocal of the thermal wave decay coefficient, as
=(f/D)1/2 because thermal oscillations in the gas, where the PA signal is generated, are not
efficiently driven, due to thermal wave decay, from deeper than L =(D/v ) 1/2 , where the
IR beam modulation frequency, f = v. With step-scan FTIRs sampling depth is constant
across the spectrum and controlled by the phase modulation frequency, fm, and given by
L=(D/ fm) 1/2 . L only defines the sampling depth if the samples absorption coefficient, ,
in the spectral region of interest, is low enough to allow light to penetrate deeper than L. If
this is not the case, the sampling depth is determined by the decay of light waves rather than
of thermal waves and is given by 1/.

APPLICATIONS AND CONCLUSIONS

Considering the photothermal mechanism alone, the photoacoustic signal is useful in
measuring the light absorption spectrum, particularly for transparent samples where the light
absorption is very small. In this case the ordinary method of absorption spectroscopy, based
on difference of the intensities of a light beam before and after its passage through the
sample, is not practical. In photoacoustic spectroscopy there is no such limitation. The signal
is directly related to the light absorption and the light intensity. Dividing the signal spectrum
by the light intensity spectrum can give a relative percent absorption spectrum, which can be
calibrated to yield absolute values. This is very useful to detect very small concentrations of
various materials.
Photoacoustic spectroscopy is also useful for the opposite case of opaque
samples, where the absorption is essentially complete. In an arrangement where a sensor is
placed in a gaseous phase above the sample and the light impinges the sample from above,
the photoacoustic signal results from an absorption zone close to the surface.

REFERENCE
Laser spectroscopy: basic concepts and instrumentation. ---------- W Demtroder.
Photoacoustics and Photoacoustic Spectroscopy ----------- (R.E. Krieg Publishing Company,
Malabar, Florida, 1980
Performance and Selected Applications of an Acousto-Optic Spectrometer -----------

Martin Hhne, Ursula Eschenauer, and Heinz W. Siesler(OSA PUBLISHING)