Sensors 2014, 14, 6165-6206; doi:10.

3390/s140406165
OPEN ACCESS

sensors
ISSN 1424-8220
www.mdpi.com/journal/sensors
Review

Quartz-Enhanced Photoacoustic Spectroscopy: A Review

Pietro Patimisco 1,2, Gaetano Scamarcio 2, Frank K. Tittel 1 and Vincenzo Spagnolo 2,*
1
Department of Electrical and Computer Engineering, Rice University, 6100 Main Street,
Houston, TX 77005, USA; E-Mail: fkt@rice.edu
2
Dipartimento Interateneo di Fisica, Universitàdegli studi di Bari Aldo Moro e Politecnico di Bari,
Via Amendola 173, Bari, I-70126, Italy; E-Mails: pietro.patimisco@uniba.it (P.P.);
gaetano.scamarcio@uniba.it (G.S.)

* Author to whom correspondence should be addressed; E-Mail: v.spagnolo@poliba.it;

Tel.: +39-080-544-2373; Fax: +39-080-544-2219.

Received: 29 November 2013; in revised form: 18 February 2014 / Accepted: 21 March 2014 /
Published: 28 March 2014

Abstract: A detailed review on the development of quartz-enhanced photoacoustic sensors

(QEPAS) for the sensitive and selective quantification of molecular trace gas species with
resolved spectroscopic features is reported. The basis of the QEPAS technique, the
technology available to support this field in terms of key components, such as light sources
and quartz-tuning forks and the recent developments in detection methods and performance
limitations will be discussed. Furthermore, different experimental QEPAS methods such
as: on-beam and off-beam QEPAS, quartz-enhanced evanescent wave photoacoustic
detection, modulation-cancellation approach and mid-IR single mode fiber-coupled sensor
systems will be reviewed and analysed. A QEPAS sensor operating in the THz range,
employing a custom-made quartz-tuning fork and a THz quantum cascade laser will be
also described. Finally, we evaluated data reported during the past decade and draw
relevant and useful conclusions from this analysis.

Keywords: quartz enhanced photoacoustic spectroscopy; quartz tuning fork; gas sensing;
mid-IR and THz laser spectroscopy
Sensors 2014, 14 6166

1. Introduction

The detection and measurement of trace gas concentrations is important for both the understanding
and monitoring of a wide variety of applications, such as environmental monitoring, industrial process
control analysis, combustion processes, detection of toxic and flammable gases, as well as explosives.
For example, trace gas sensors capable of high sensitivity and selectivity are required in atmospheric
science for the monitoring of different trace gas species including greenhouse gases and ozone, and in
breath diagnostics, nitric oxide, ethane, ammonia and numerous other biomarkers. Quantitative and
qualitative gas sensors can be categorized into four general groups: analytical sensors (principally
gas-chromatography and spectrometry), electrochemical, semiconductor sensors and laser optical
absorption sensors. The sensor classification is primarily based on the physical mechanism that is used.
Analytical techniques do not offer real-time response, tend to be costly, invasive and occupying a large
spatial footprint. Electrochemical gas sensors can be relatively specific to individual gas, have usable
resolutions of less than one part per million (ppm) of gas concentration, and operate with very small
amounts of current, making them well suited for portable, battery powered instruments [1]. However,
they experience hysteresis and are influenced by water humidity. Moreover, one important
characteristic of electrochemical sensors is their slow time response: when first powered up, the sensor
may take several minutes to settle to its final output value and when exposed to a mid-scale step in gas
concentration, the sensor may take tens of seconds to reach 90% of its final output value. Techniques
based on laser absorption spectroscopy (LAS) for trace gas sensing, compared to other techniques, are
considerably faster with response times of <1 s, suffer from minimal drift, offer high gas specificity,
capable of part-per-quadrillion (ppq) detection sensitivity [2] and permit real time in-situ
measurements. The principle of molecular absorption is based on the transitions that an
electromagnetic wave causes in a chemical species. If a molecule is irradiated by infrared light, it is
excited to a rotational-vibrational energy level manifold. Absorption lines are specific for each
chemical species. To-date LAS has been developed mostly in the spectral region from 3 to 12 μm,
which covers a substantial spectral range of fundamental transitions in the so called molecular
finger-print region. Further extension into the vibrational overtone (1–2.5 μm), electronic (UV-Vis)
and rotational (THz range) spectral range is also feasible.
The detection sensitivity of spectroscopic sensor systems that employ semiconductor lasers as a
light source is limited by the available optical power, especially when dispersive elements and
multi-detector arrays are used to analyze the light transmitted through the gas sample. In the near-IR
spectral range optical parameter oscillators or conventional diode laser are typically the light source of
choice. In the mid-IR and THz spectral regions quantum cascade lasers (QCLs) and interband cascade
lasers (ICLs) are the optimal choice, due to their high output power, compactness, narrow spectral
linewidth and broad wavelength tunability [3–5]. Two main QCL configurations are used:
(1) distributed feedback (DFB) QCLs having a Bragg reflector built on top of waveguide, which forces
the QCL to operate in single axial mode operation. QCLs are tuned by keeping the device operating
temperature fixed and changing the current or vice versa, keeping the current fixed and changing the
temperature; or (2) an external cavity QCL (EC-QCL), in which the quantum cascade device is the
laser gain medium and mirrors are arranged in a configuration external to the laser to create an optical
Sensors 2014, 14 6167

cavity. By replacing one of the external cavity mirror with a high quality diffraction grating, it is
possible to tune the QCL emission wavelength over >15% of its central value.
LAS-based techniques offer not only excellent sensitivity and selectivity, but also long effective
optical pathlengths, compactness, mechanical stability, versatility and cost effectiveness. In the case of
cavity ring down spectroscopy (CRDS) an optical cavity with two concave mirrors with low loss and
high reflectivity (>99.9%) provides a long optical path of up to several kilometers. A light pulse is
injected into the cavity through one of the mirrors and inside the cavity, multiple reflections occur.
After each reflection, leakage radiation from the cavity is registered by means of an appropriate
photodetector [6]. A modification of the CRDS is cavity enhanced absorption spectroscopy (CEAS) in
which the radiation is injected at a very small angle respect to the cavity axes which results in the
formation of a dense structure of weak optical axial modes that makes the entire system more robust
against instability in both the cavity and laser spectrum [7]. The idea of integrated cavity output
spectroscopy (ICOS) is similar to CEAS. However, the measurement procedure is based on the
comparison between the signal amplitude both at the input and the output of the cavity [8]. Both
techniques require precise information about mirror reflectivity, a sensitive photodetector with a
fast-response, perfect optical alignment and the use of long optical pathlengths. One of the most robust
and sensitive trace-gas optical detection techniques is photo-acoustic spectroscopy (PAS), which is
capable of extremely high detection sensitivities with a compact and relatively low-cost absorption
detection module (ADM) [9].

2. Photoacoustic Spectroscopy

This technique is also based on an optical absorption process, such as CRDS, ICOS and CEAS, but
differs in the physical phenomenon used for the detection of the absorption signal. When light at a
specific wavelength is absorbed by the gas sample, the excited molecules will subsequently relax to the
ground state either through emission of photons or by means of non-radiative processes. These
processes produce localized heating in the gas, which in turn results in an increase of the local
pressure. If the incident light intensity is modulated, the generation of thermal energy in the sample
will also be periodic and a pressure wave, i.e., a sound wave, will be produced having the same
frequency of the light modulation. The PAS signal can be amplified by tuning the modulation
frequency to one of the acoustic resonances of the gas sample cell. The key advantage of this technique
is that no optical detector is required and the resulting sound waves can be detected by a commercial
hearing aid microphone.
The photoacoustic signal S can be expressed by the relation:
(1)
where C is the instrumental constant, P is the laser power and α is the absorption coefficient that is
equal to:
(2)
where σ is the cross section of the optical transition, c is the concentration of the target gas and Ntot is
the total number of molecule per unit volume. From Equation (1) it follows that there is linear
relationship between the sample concentration and the photoacoustic signal. The minimum optical
Sensors 2014, 14 6168

absorption coefficient αmin detectable with a PAS based sensor is determined by the condition S = N,
where N is the noise level, which is assumed to be independent from the optical excitation. Hence, the
minimum detectable concentration cmin can be expressed by using Equation (2) as:

(3)

The instrumental constant C in Equation (1) depends on the cell size and geometry, the modulation
frequency of the radiation, the efficiency of the transducer and the quality factor Q of the acoustic
resonance defined by:

(4)

where f0 and ΔfFWHM are the resonant frequency and the full width at half maximum (FWHM) of the
resonance profile, respectively. The quality factor Q can be experimentally measured and typically
ranges from 40 to 200 and the resonant frequency from the measured values of Q and f0 typically fall
in the ranges 40–200 and 1,000–4,000 Hz, respectively. The PAS signal is proportional to the effective
integration time t = Q/f0. One of the highest reported values is t = 56 ms. Achieving longer integration
times in a gas-filled resonator is problematic because of intrinsic losses related to gas viscosity and
other relaxation processes.
Continuous-wave single-mode diode lasers and optical parameter oscillators in the near-IR and
QCLs in the mid-IR have been successfully applied in PAS [9]. Compact photoacoustic gas sensors
based on broadband IR sources have been reported [10]. Resonant PAS cells and optical fiber
amplifiers have been developed to enhance the PAS detection sensitivity [11]. The three main noise
sources are: (i) noise caused by the radiation that is incident upon the walls of the PAS absorption cell;
(ii) non-selective absorption of the gas cell window, and (iii) external acoustic noise. In order to
improve the signal-to-noise ratio (SNR), different designs for PAS cells have been proposed and
implemented including a resonant cell with acoustic buffers [12], windowless and a differential cell. A
differential cell includes two acoustic resonators equipped with microphones having the same
responsivity at the resonance frequency of the cell. Since the laser light excites only one of the two
resonators, the difference between the two signals removes noise components that are coherent in both
resonators [13].
PAS has been successfully applied in trace gas sensing applications, which include atmospheric
chemistry, volcanic activity, agriculture, industrial processes, workplace surveillance, and medical
diagnostics. For instance, PAS has been used to monitor nitric oxide (NO) from vehicle exhaust
emissions, which contributes to respiratory allergic diseases, inflammatory lung diseases, bronchial
asthma and the depletion of ozone [14]. In medicine, PAS has been used to monitor drug diffusion
rates in skin [15] and to detect trace concentrations of disease biomarkers, such as ethylene (C2H4),
ethane (C2H6), and pentane (C5H12), which are emitted by UV-exposed skin [16]. Other applications
include monitoring respiratory NH3 emission from cockroaches as well as detecting the intake of
prohibited substances by athletes [17]. Low cost portable PAS sensors have been on the market,
examples of which include smoke detectors, toxic gas monitoring, and oil sensors for monitoring
hydrocarbons in water.
Sensors 2014, 14 6169

3. Quartz-Enhanced Photoacoustic Spectroscopy

Quartz-enhanced photoacoustic spectroscopy (QEPAS) is an alternative approach to photoacoustic

detection of trace gas utilizing a quartz tuning fork (QTF) as a sharply resonant acoustic transducer to
detect weak photoacoustic excitation and allowing the use of extremely small volumes [18,19]. Such
an approach removes restrictions imposed on the gas cell by the acoustic resonance conditions. A
quartz crystal is a natural candidate for such an application because it is a low-loss and low-cost
piezoelectric material. High-Q quartz crystals are employed as a frequency standard in clock, watches
and smart phones. Usually QTFs with a resonant frequency of 215 or ~32,768 Hz are used. QTFs
possess a Q ≈ 100,000 or higher when encapsulated in vacuum and a Q ≈ 10,000 at normal
atmospheric pressure. Therefore, the corresponding energy accumulation time at atmospheric pressure
is t ≈ 320 ms.
Acoustically, QTF is a quadrupole, which provide good environmental noise immunity. In fact, the
width of the QTF resonance at normal pressure is ~4 Hz, so only frequency components in this narrow
spectral band can produce efficient excitation of the QTF vibrations. Sound waves in air at 32 kHz
have an acoustic wavelength ~1 cm, and thus, if produced by external acoustic sources, such waves
tend to apply a force in the same direction on the two QTF prongs positioned at a ~1 mm distance. As
a result, such sound waves do not excite the piezoelectrically active mode in which the two prongs
move in opposite direction and zero electrical response is produced. Hence, there is only one way to
cause the QTF to resonate via the photoacoustic effect to produce sound waves from a source located
between the two QTF prongs. The standard way to realize such a condition is for the excitation laser
beam to pass through the gap between the prongs without touching them.
The generation of a photoacoustic wave involves the energy transfer from internal to translational
molecular degrees of freedom. If a rotational-vibrational state is excited, a collision-induced
vibrational to translation (V-T) relaxation follows, with a time constant that for a particular molecule is
dependent on the presence of other molecules and intermolecular interactions. QEPAS measurements
are usually performed at a detection frequency of about 32 kHz and are more sensitive to the V-T
relaxation rate compared to the conventional PAS which is commonly performed at f0 < 4 kHz. In case
of slow V-T relaxation with respect to the modulation frequency, the thermal waves in the gas cannot
follow fast changes of the laser induced molecular vibration excitation. Thus, the generated
photoacoustic wave is weaker than it would be in case of fast V-T energy equilibration [20]. For
instantaneous V-T relaxation, the detected photoacoustic signal can be expressed in the same way of
the PAS:

(5)

Q typically ranges from 104 to 105, depending on the carrier gas and the gas pressure.

3.1. QEPAS Sensor

A sketch of a typical QEPAS sensor, originally proposed in [18–20] and used in most reported
QEPAS sensor systems, is shown in Figure 1. The optical components can vary depending on the
spectral range, target molecule and the excitation laser. Typically, the wavelength of the laser is varied
Sensors 2014, 14 6170

by changing the driving current when the temperature of the laser is fixed. This is the configuration
used if employing for example a DFB QCL as the light source, with an integrated Peltier cooler and a
temperature controller system. When an EC-QCL is used, both temperature and current are fixed, and
the optical frequency can be scanned by applying a modulated voltage to a piezoelectric translator (not
shown in the figure) attached to the diffraction grating element of the EC-QCL.

Figure 1. Schematics of a standard QEPAS based sensor. PD – Photodetector,

CEU – Control Electronic Unit providing laser current and temperature, wavelength tuning
& and two lock-in detection circuits.

A beam-splitter can be used to split the incoming laser beam, sending a small portion to a reference
cell full with a high concentration of the targeted trace gas. The light exiting the reference cell is
detected by a photodetector and the absorption signal demodulated at 3f by means of a lock-in
amplifier. In this way, a 3f wavelength locking technique can be implemented to lock the laser
wavelength to the absorption peak line of the targeted molecule. The 3f component crosses zero at the
line center and is linear with detuning. If the detuning is sufficiently small, this feedback signal is used
in a wavelength stabilization closed-loop. The laser beam passes through the beam-splitter and is
focused between the two prongs of the QTF normally by using a lens. The wavelength modulation
technique is implemented by applying a sinusoidal dither to the laser current at half of the QTF
resonance frequency; a control electronic unit (CEU) is used to acquire the signal from the QTF that is
demodulated at the QTF resonance frequency by means of a lock-in amplifier. The lock-in amplifier is
usually controlled via a PC or a laptop computer through a USB NI card or RS232 communication.
Sensors 2014, 14 6171

3.1.1. Quartz Tuning Fork: Resonant Properties and Noise

QTFs can be designed to resonate at any frequency in the 4–200 kHz range and beyond, since
resonance frequencies are defined by the properties of the piezoelectric material and by its geometry.
The interaction between the laser modulated beam and a trace gas leads to the generation of acoustic
waves that mechanically bend the QTF prongs. Hence, the electrode pairs of the QTF will be
electrically charged due to the quartz piezoelectricity. Piezoelectricity is the coupling between internal
dielectric polarization and strain, and is present in most crystals lacking a center of inversion
symmetry. When a stress is applied to these materials, it induces a displacement of charge and a net
electric field. The effect is reversible: when a voltage in applied across a piezoelectric material, it is
accompanied by a strain. Due to this intrinsic coupling of strain and charge displacement a QTF can be
modeled both electrically and mechanically, each prong being modeled as a slab of dimension
w × y0 × t0, as shown in Figure 2.

Figure 2. Schematic of a quartz tuning fork. Each prong can be modeled as a rectangular
bar of dimension w y0 t0 (dotted lines). Inset: a top view of the tuning fork with the
electrical configuration for the electrodes A and B.

t0
w0

y0

A B

Both mechanical motion and electrical response can be modeled using differential equations, having
equivalent mathematical forms. Thus, the QTF is both a circuit with capacitance C, resistance R and
inductance L, and equivalently a mass m on a spring, with spring constant k and damping factor β. The
two domains can be coupled through a relation, in which the force driving the QTF is proportional to
the driving voltage. Hence, a voltage signal measured from the QTF can easily translate into the force
on it. The circuit schematic used to characterize the QTF is shown in Figure 3. An optimum approach
is to acquire the QTF electrical response using an ultra-low transimpedance amplifier with feedback
Sensors 2014, 14 6172

resistor Rf = 10 MΩ. Feedback maintains a zero voltage between the QTF electrodes and so that the
influence of the parallel stray capacitance Cp is neutralized.
In this condition, the QTF model is reduced to an RLC series circuit and the resonant frequency is
given by:

(6)

and the Q factor is:

(7)

while the impedance of the RLC circuit at the resonance condition is equal to its resistance.

Figure 3. Schematic of the circuit used to characterize a QTF.

Quartz Tuning Fork Rf

Vin = A·sin(ωt)
L C R

Vout
R1

R2

CP

The QEPAS sensor noise measured at the amplifier output at the resonant frequency f0 is primarily
determined by the thermal noise of the equivalent resistor R [17]:

(8)

where VN is the voltage noise at the transimpedance amplifier output, Δf is the detection bandwidth and
T is the QTF temperature. The feedback resistor also introduces noise, which is several times lower
than the thermal QTF noise and can be neglected for typical values of R in the range 10–100 KΩ. The
electrical parameters of the QTF can be determined by using a CEU, which applies an ac voltage V to
the circuit depicted in Figure 3, while scanning the applied voltage frequency f. The maximum of the
I(f) function, where I is the QTF current and f is the modulation frequency of the applied voltage,
yields the resonant frequency f0. In this way, R and Q are determined by using the Equation (7) and
the relation:

(9)
Sensors 2014, 14 6173

The available resonant frequencies of the QTF can be calculated by considering an approximation
in which each prong of the fork is considered to behave as a cantilever vibrating in the in-plane
flexural modes of the tuning fork. The first two flexural modes are shown in Figure 4.

Figure 4. (a) First in-plane vibrational mode of a tuning fork. (b) Third in-plane
vibrational mode of a tuning fork.

In the first flexural mode, the tines move in opposite directions and the center of mass of the QTF
remains unchanged. The flexural mode vibration can be modeled by considering that each prong of the
tuning fork behaves as a clamped beam. When the force is removed from the displaced beam, the beam
will return to its original shape. Assuming the elastic modulus, inertia and cross sectional area are
constant along the beam length, the equation for that vibration is given by the following fourth-order
differential equation, according to the Euler-Bernoulli approximation:

(10)

where ρ is the density of the material, E the Young modulus of the material, t is the time, A = w y0
and x and y directions in the plane of the QTF. Equation (10) can be solved by separation of variables,
assuming that the displacement can be separated into two parts; one that depends on position and the
other on time. This leads to a simplified differential equation for the y direction that can be solved by
superimposing boundary conditions. These boundary conditions come from the support of the QTF.
The fixed end must have zero displacement and zero slope due to the clamp, while the free end cannot
have a bending moment or a shearing force (free-clamped boundary conditions). The general solution
is a linear combination of trigonometric equations leading to the frequency equation for the cantilever
beam [21]:
(11)
where kn are the wavenumbers related to the eigenfrequencies fn, given by the following expression:

(12)

where and . U-shaped QTFs are mass-produced as mentioned previously

on page 5 for timing application used in electronic clocks and smartphones. The standard QTF has a
Sensors 2014, 14 6174

resonant frequency of ~32 KHz, with a gap between the prongs of ~300 µm, and prongs that are
3.2 mm long and 0.33 mm wide, as depicted in Figure 2. Such QTFs have been widely used in all
mid-IR QEPAS based sensors reported in the literature to-date, because of their commercial
availability and ultra-low cost. Chromium/gold layer are deposited on both sides of the QTF to create
electrodes, which collect the electrical charges induced by the mechanical deformation. The first three
solutions of Equations (11) and (12) are shown in Table 1:

Table 1. n values and the resonant frequencies fn for the standard QTF fork calculated from
Equation (3.8).
n fn (Hz)
1.194 31978
2.988 200263
5 560764

When a QTF vibrating at harmonics oscillations of small amplitude is immersed in a fluid medium,
it tends to induce a motion in the fluid, which gives rise to an energy loss and additional inertia. The
reaction force is hence composed of a resistive part, which leads to energy dissipation by acoustic loss
and a reactive part, which gives rise to an additional inertia to the vibrating QTF body. For these
conditions, Equation (10) can be modified by considering a term which includes damping effects
(damping parameter Cd) and an added mass u per unit length [21]:

(13)

By assuming in a first approximation that damping remains small and u << ρA it can be shown that
an added mass causes a shift of the QTF resonance frequency, Δf with respect to that in vacuum:

(14)

The exact derivation of the added mass is a complicated problem even for a simple structure. For a
vibrating prong in steady motion, the added mass is proportional to the density ρ0 of the fluid medium.
Since there is a linear relationship between the pressure and the density in a gas, we obtain that Δf
varies linearly with gas pressure. However, the fluid damping influences negatively the quality factor
Q of the flexural beam. In fact, the reaction force due to the presence of the gas acting on a vibrating
QTF leads to energy dissipation by means of an acoustic loss. Assuming that the fluid drag force is the
dominant damping source, i.e. the resonator is isolated from other objects so that other damping effects
need not to be considered, and the fluid damping parameter can be expressed as [22]:
(15)
where µ0 is the viscosity of the fluid and where the linearity between the density and the pressure in a
gas applies again. Hence the influence of fluid damping on the Q can be expressed in terms of the
energy loss 1/Q(P) at a gas pressure, P:

(16)
Sensors 2014, 14 6175

where Q0 is the tuning fork Q factor in vacuum, which depends only on the internal losses and losses
added by the electrical circuit of the transimpedance amplifier. By using Equation (15), Q(P) can be
described as:

(17)

Hence, the dependence of QEPAS detection sensitivity upon the trace gas concentration in a
specific absorbing gas sample is a function of the sample pressure. This dependence is influenced by
different parameters: (i) the Q factor of a QTF decreases rapidly with increasing pressure due to energy
losses by the mechanical viscosity and friction losses via the trace gas; (ii) at low gas pressures the
collisional line broadening of the absorption peak is less than Doppler broadening Hence, the merging
of closely spaced absorption lines should be taken into account at higher pressures; (iii) V-T relaxation
rates are faster at higher pressures which is in competition with the opposite trend of the Q factor; and
(iv) the speed of sound depends on the gas pressure.

3.1.2. Wavelength Modulation Detection

The wavelength modulation (WM) technique is generally used to improve the QEPAS SNR and to
minimize external acoustic noise for a QEPAS based sensor system.. The WM description is based on
an intensity representation of an optical wave, so that only the absorption of the sample is considered
and dispersion effects due to the sample can be neglected. The description is based on the
instantaneous laser frequency:
(18)
where υ0 is the optical carrier frequency and ω = 2πf is the modulation angular frequency due to the
laser injection current modulated at the same angular frequency. In addition to frequency modulation,
the current waveform applied to the QCL produces a sinusoidal modulation of the laser intensity and is
given by:
(19)
The amplitude ΔI of the sinusoidal intensity modulation is determined by the slope of the laser
power versus the current characteristics, which is assumed constant across a wavelength scan. The
instantaneous laser frequency interacts with the absorption feature. Expanding the absorption
coefficient α(ν(t)) for a small Δν we obtain:

(20)

where α0 can be considered to be the background absorption contribution. The laser is modulated both
in intensity and in wavelength simultaneously. Thus, assuming a small absorption Iabs, from the
Lambert-Beer law we have:

(21)
Sensors 2014, 14 6176

L is the effective length over which the absorption takes place to produce an acoustic wave detectable
by the QTF (in other words, L is comparable with the thickness t0 of the QTF. Hence, the 1ω-signal,
S1ω, is given by:

(22)

and the 2ω-signal S2ω is given by:

(23)

This result shows that the background absorption contributes to the S1ω, whereas it does not
contribute to S2ω. If we assume that the absorption coefficient has a pure Lorentzian lineshape, S1ω has
a pure first derivative line-shape with a constant background; S2ω consists of two terms: the first term,
arising from a residual amplitude modulation is proportional to the first derivative, whereas the second
is the second-derivative expression arising from the laser wavelength modulation. Hence, S2ω is not a
pure second derivative of the Lorentzian lineshape but is distorted by a contribution originating from
the residual amplitude modulation. This distortion does not affect the peak position of S2ω since the
first derivative of the Lorentzian lineshape vanishes when υ = υ0.

Figure 5. 1f-QEPAS (a) and 2f-QEPAS (b) spectral scans of 2.6 ‰ of CO2 in N2 at a gas
pressure of 50 Torr of a CO2 line centered at 2,311.515 cm−1. Blue lines highlight the
strong background of the spectral 1f-QEPAS acquisition.
2
a) 3
b)
1
1f-QEPAS Signal (V)

2f QEPAS Signal (V)

2
0

-1
1
-2

0 -3

-4
0 10 20 30 40 50 0 10 20 30 40 50
Scan time (s) Scan time (s)

The generated QEPAS signal is usually demodulated by means of a lock-in amplifier both at the
fundamental frequency f or the successive harmonics nf. When the laser light is modulated at the
resonant frequency f0 and QEPAS signal is demodulated at the same frequency, the demodulated signal
is usually called 1f-QEPAS signal, while when the laser light is modulated at the f0/2 and QEPAS
signal is demodulated at f0, the demodulated signal is referred to 2f-QEPAS signal. In this case, the
QTF detects sound oscillations at the second harmonic of the modulation frequency caused by the
double intersection of the absorption line by the laser line during a modulation period. In Figure 5
1f-QEPAS (2f-QEPAS) spectral scan of a 2.6 ‰ of CO2 in N2 mixture is depicted at a total gas pressure
of 50 Torr, obtained by current modulation at ( ) and a
peak-to-peak voltage amplitude of 2.8 V acquired by using a bare QTF (i.e., without mR tubes) and a
Sensors 2014, 14 6177

CW DFB QCL targeting the CO2 (0111)–(0110) P(29) rotational-vibrational transition centered at
2,311.515 cm−1 and with a linestrength of 7.458  10−20 cm/mol.
A strong background signal was observed for the 1f approach, originating from stray light ending up
on the walls of the acoustic detection module. This is confirmed by the observation that the amplitude
of this offset strongly increases with a misalignment of the laser beam in lateral directions so that the
beam wings touch the QTF. Instead, it was experimentally observed that the 2f approach is
background-free. Distortions in the demodulated signal displaying an asymmetry on both side of the
spectrum around the peak (see Figure 5b) can be associated to an amplitude intrinsic modulation
contribution, which is introduced by current modulation. The laser wavelength modulation amplitude Δf
and light intensity modulation ΔI must be optimized at each gas pressure for a highest 2f-QEPAS signal.

3.1.3. Amplitude Modulation Detection for Broadband Absorbers

Vibrational spectra of most molecules consisting of more than five atoms are so dense that infrared
absorption spectra of such polyatomic molecules consist of 100–200 cm−1 broad bands. Spectroscopic
identification of these species requires laser excitation sources with a wide spectral coverage.
However, distributed feedback (DFB) or Fabry-Perot (FP) QCLs cannot be wavelength modulated
with a sufficient spectral tuning coverage for broadband absorption features. Thus, QEPAS detection
of such molecules will require amplitude modulation (AM) of the laser radiation. The laser is operated
at f0 by means of square wave amplitude current modulation and the QEPAS signals are detected by a
lock-in amplifier at the same f0 frequency. Unlike WM QEPAS, AM QEPAS is not background free.
Residual absorption of laser radiation by the cell windows as well as scattered radiation absorbed
inside the gas cell produce a sound at the TF resonant frequency, thus generating a coherent
background. However, this background can be stable over several hours, which allows background
subtraction. Typically, for every spectral point, both signal and background components normalized to
the laser power are acquired. In post-processing, the in-phase and the quadrature components of the
photoacoustic signal were calculated, respectively and by vector subtraction, it is possible to remove
the background signal [22–25].

3.2. On-Beam QEPAS

To enhance the QEPAS signal and to confine the sound wave a micro-resonator (mR) is employed.
The typical acoustic mR consists of two thin tubes aligned perpendicular to the QTF plane. The
on-beam coupled resonator system as depicted in Figure 6 consisting of a QTF and a mR is called a
spectrophone or acoustic detection module (ADM). This innovative approach is described in detail
in [18–20,23–50]. It is critical that the laser beam that enters the mR does not touch the mR walls in
order to avoid photothermal effects.
The QTF resonant parameters change when it is coupled to the mR. The decrease of the Q factor
provides a measure of acoustic coupling between the QTF and the mR, since the high-Q QTF loses
energy primarily via coupling to the low-Q mR oscillator. This can be explained by considering that a
QTF is acoustically a quadrupole and the mR is an acoustic dipole with a higher acceptance
bandwidth, which results in a reduction of the Q factor of the acoustically coupled system. A QTF
integrated into a mR has a higher fundamental frequency indicating that an additional force constant is
Sensors 2014, 14 6178

added due to acoustic coupling. If we consider in a first approximation that the two parts of the mR can
be considered as a single tube, each tube cut to a length l~λs/4, where λs is the sound wavelength,
behaves as a half-wave resonator. Further analysis and experimental studies have shown that the
QEPAS signal is in fact stronger when l~λs/2 suggesting that the gap between the tubes is big enough
to make them quasi-independent. More detailed studies showed that the optimum length is in fact
between λs/4 and λs/2 because of the interaction of mR tubes and acoustic coupling to the QTF [51,52].

Figure 6. Schematic of an on-beam QEPAS configuration. Two micro-resonator tubes are

aligned perpendicular to the QTF plane to probe the acoustic vibration excited in the gas
contained inside the ADM.

Dong et al. [40] reported a detailed performance evaluation of the QEPAS sensor operation as a
function of the geometrical mR parameters (tube diameter, tubes length and gaps between the QTF
surface and tube end facets) and derive conclusions regarding the optimum mR configuration
depending on the specific application, the operating pressure and the acoustic coupling. By a selective
choice of the size, the acoustic resonance in the mR tubes can significantly improve the sensor
performance. The best SNR of the QEPAS signal is achieved with tubes having a length of 4.4 mm, an
internal diameter of 0.6 mm and an external diameter of 0.71 mm. The gaps between each side of mR
tubes and the QTF surface were in the 30–50 µm range. This mR tubes length is significantly shorter
than the half-wavelength of sound estimated by considering the speed of sound (340 m/s) in pure
nitrogen at 293 K [38]. At the optimum tube length, the effects of acoustic resonance dominate and the
Q factor of the mR filled with gas increases with its diameter. By using longer mR tubes, the SNR
increases when the tube diameter is reduced and resonant effects in the mR are not strongly
pronounced. Therefore, the volume of the excited gas becomes the primary factor and causes the
Sensors 2014, 14 6179

QEPAS signal to increase when the absorbed optical energy is distributed over a smaller amount of
gas. For a mismatched condition, the mR tubes simply confine the sound wave and do not exhibit a
pronounced resonant behavior. By increasing the external diameter (thicker mR tubes) the acoustic
coupling is higher, which result in a lower Q factor. Tubes with a larger inner diameter match the QTF
frequency when reduced to a shorter length. In fact, with a larger tube diameter the gap between two
mR tubes becomes less important and the system moves closer to the configuration in which we can
neglect the gap between the two parts of the mR tubes (l~λs/4) [53]. This configuration has the
advantage of easier optical alignment, but the spectrophone is more sensitive to environmental acoustic
noise due to a lower Q factor. A record SNR improvement in SNR by a factor of ~30 was achieved by
using tubes having a length of 4.4 mm and an internal diameter of 0.6 mm, for a spectrophone
operating in the pressure range 500–700 Torr [40].
In the following, a simplified model which considers the total momentum of a pressure force acting
on the two prongs of the QTF is presented. The main assumptions are: (i) two prongs, which radiate as
point sources and create divergent spherical-shaped sound waves (monopole approximation); (ii) the
intensity of the pressure wave decreases as the inverse of the distance and is assumed to be constant
along the thickness of each prong. In this approximation only force lines that lie on y-z plane (the
plane that contains the two prongs) are considered; (iii) acoustic coupling between two oscillating
prongs can be neglected (small oscillations approximation). The acoustic source is centered on the
z-axis, as shown in Figure 7. By assuming that the beam waist of the focused laser beam is equidistant
from the two prongs, the total momentum Mtot can be expressed by the following relation:

(24)

where is the acoustic pressure on the infinitesimal area element dz of the surface and

r= is the prong distance from the sound wave point source; is the sine

of the angle between the force vector acting on the prong and the lever arm; P0 is the initial value of
the intensity of the pressure wave; d is the gap between the two QTF prongs.

Upon integration, an expression for Mtot as a function of h (the vertical position) can be found:

(25)

To validate the model and study the dependence of the QEPAS signal strength (which is
proportional to the total momentum generated by the pressure wave) as a function of the vertical
position of the laser beam, the experimental data obtained by employing a QEPAS sensor with a
32.8 kHz QTF, was fitted using Equation (25). The experimental results were acquired by detecting
H2O in N2 at a concentration of 2% of at a total gas pressure of 75 Torr using a peak-to-peak voltage
Sensors 2014, 14 6180

amplitude of 4.2 V and a EC-QCL emitting at 10.54 µm for targeting a H2O line centered at
948.263 cm−1. The experimental data and the obtained best fit by using Equation (25) are shown in
Figure 8.

Figure 7. QTF with the main parameters employed for calculations and related to the
coordinate system used. The origin of the y-axis is centered between the prongs.

Figure 8. Normalized experimental results (dots) of the QEPAS signals as a function of the
vertical position of the QTF. Data are obtained by detecting a concentration of 2% H2O in
N2 at 75 Torr and by using an on-beam QEPAS sensor system configuration. The solid line
is the best fit curve obtained using Equation (3.21).

1.0
Normalized QEPAS signal

0.8

0.6

0.4

0.2

0 1 2 3 4 5
h (mm)

The experimental data depicted in Figure 10 was normalized to the highest QEPAS signal. The
theoretical model can thus accurately predict the experimentally observed optimal vertical position of
the laser beam.
A more detailed and exhaustive theoretical model for the determination of the beam position of the
laser beam that maximizes the QEPAS signal was proposed by Petra et al. [54]. The model consists of
three stages. First, Petra et al. calculate an explicit formula for the acoustic pressure wave by using the
cylindrical symmetry of the laser beam and the narrow width of the tuning fork resonance, to reduce
the inhomogeneous wave equation to a Bessel equation. The model shows that the amplitude of the
pressure wave is proportional to the laser modulation frequency. Then, they use the Euler-Bernoulli
Sensors 2014, 14 6181

equation to model the resonant vibration of the prongs of the QTF. Finally, they use the well-known
electromechanical relationships of for QTFs to calculate the piezoelectric current generated by the
mechanical vibration. To derive analytical solution for this model, they ignored the effect the QTF has
on the acoustic pressure wave and assumed that the piezoelectric response of the tuning fork can be
obtained by modeling each prong individually. In spite of these simplifying assumptions, an excellent
agreement between theory and experiments was found and the optimal vertical position of the focused
laser beam occurs at y ~ 3.3 mm in good agreement with the result of our simplified model.

3.3. Off-Beam QEPAS

The on-axis QEPAS configuration has several disadvantages, such as: (i) the resonant acoustic
wave condition was not exactly obtained; (ii) the open-ended tubes introduce sound energy-losses; (iii)
the gap between the QTF prongs is only ~300 µm wide, which limits the inner diameter of the mR and
thus the size of the laser beam that passes through the tubes; An alternative configuration called
“off-beam QEPAS” was first reported in [55]. In off-beam-QEPAS, the laser beam and the QTF are
separated by a physical barrier, i.e., the microresonator walls and the QTF senses the pressure in the
microresonator through a small aperture in its center. Thus, in off-beam-QEPAS configuration, the mR
is a single tube and its length determines the first longitudinal mode of the acoustic wave at f0. For this
mode, the resonant acoustic pressure antinode is at the center of the mR. Hence a small slit is made in
the middle of the mR and the QTF is coupled to the mR by placing it external to the mR tube close to
the centrally located mR aperture. A sketch of the off-beam configuration is shown in Figure 9.

Figure 9. Sketch of an off-beam QEPAS spectrophone configuration. The micro-resonator

tube is located close to the prongs of the QTF without touching them. The green circular
lines indicate the acoustic wavefronts.

The off-beam-QEPAS configuration results in certain technical advantages as it facilitates the optical
alignment and allows more flexibility in the selection of QTF dimensions. In off-beam-QEPAS, the
acoustic oscillations of the gas are excited in the mR by the intensity modulation induced by the externally
located laser source. The photoacoustic signal amplitude, A in the mR can be expressed as [56]:
Sensors 2014, 14 6182

(26)

where C(f) is a geometrical parameter which describes the characteristics of the mR at a given
frequency f, that is usually the same as the QTF resonant frequency f0 or its higher harmonics. The
acoustic oscillations in the mR give rise to sound waves radiated via a slit at its center and are detected
by the QTF placed outside the mR, close to the slit, The off-beam-QEPAS signal is generated at the
QTF resonant frequency f0 , which is proportional to the amplitude of the photoacoustic signal as
described by Equation (3.22). To maximize sound energy coupling, the distance between the mR and
the QTF must be carefully chosen, since too long a distance will decrease the acoustic coupling
between mR and QTF, while too a short distance will dampen the QTF vibration because of viscous
drag. K. Liu et al. [55] have shown that the close proximity of the QTF to mR results in optimum
acoustic coupling, and therefore a higher QEPAS signal and SNR. At the same time, viscous drag in
the air layer between the QTF and mR reduces the Q factor and the SNR increases up to a gap of 5 µm
and then decreases for a wider QTF gap. The decrease of the QTF Q factor in the distance between mR
and the QTF can be approximated by an exponential decay function. A drop in the Q factor from
13,000 to 8,000 is observed indicating relatively weak mR coupling to the QTF compared to the
on-beam configuration, where the Q changes from 13,000 to as low as 1,380. A maximum
off-beam-QEPAS signal was obtained when the mR slit was positioned 1 to 1.5 mm below the QTF
opening, as observed in the case of the on-axis QEPAS configuration (see Figure 8). In [57] Liu et al.
performed an experimental investigation of the dependence of the OB-QEPAS signal as a function of
the mR length and inner diameter. They observed that the inner diameter-to-optical length ratio
linearly increases with the inner diameter. Once the inner diameter is chosen for a specific application,
the optimal ratio can be determined. In addition, for efficient coupling of the acoustic signal from the
mR to the QTF via a slit, it is also necessary to optimize the slit size. A small slit size limits the
coupling of the acoustic energy, while a large slit size disperses the output sound energy. Varying the
tube length shifts the resonant frequency of the mR and the QTF operates as a fixed-frequency probe.
By using the theory of finger-holes in woodwind instruments it is possible to find a relation between
the tube length and the mR resonance. The off-beam-QEPAS signal as a function of the resonant
frequency calculated for each mR length exhibits a Lorentzian profile, in good agreement with a
classical driven oscillator [38], centered at f = 32.11 kHz with a FWHM = 5.78 kHz corresponding to a
Q = 5.6. According to this theory, the tube length corresponding to f0 = 32,750 Hz is l = 7.56 mm. Liu
et al. found experimentally an optimal slit width of ~ 0.15 mm with a length of ~ 0.4 mm, for a mR
with an outer diameter of 0.7 mm, an inner diameter of 0.45 mm and a length of 8 mm [55]. For these
optimal conditions, a photoacoustic signal of ~15.7 times higher than that corresponding to a QEPAS
system using a bare QTF is obtained.
The SNR is reduced by a factor of ~1.7 at atmospheric pressure for off-beam-QEPAS as compared
to the on-beam design. However, off-beam-QEPAS is more flexible in terms of the QTF geometry
employing custom-made QTFs, with a smaller gap between the prongs without complications related
to using an optimized excitation laser pump beam. An off-beam-QEPAS spectrophone is also
technologically easier to assemble and align.
A low-cost UV-LED (compared to the diode lasers and QCLs) has been recently employed as light
source in an off-beam-QEPAS setup for ozone detection and a detection limit of 1.27 ppm corresponding
Sensors 2014, 14 6183

to a normalized noise equivalent absorption (NNEA) parameter of 3.02  10−8 cm−1W/Hz−1/2 was
achieved [58,59].

3.4. Fiber-coupled QCL-QEPAS

Enhanced versatility of QEPAS sensor systems in terms of flexible laser beam guidance and
compactness can be obtained with optical fiber delivery of the laser source. Compact sensors with
simple optical alignment have been realized by employing a single mode fiber delivery system of a
near-IR laser source and a QEPAS ADM. The extension of this approach to mid-IR QEPAS sensors is
limited by the lack of low-loss, single-mode optical fibers. A single spatial mode laser beam is
mandatory for QEPAS sensing since the radiation blocked by the ADM creates an undesirable
background that is usually several times larger than the QTF thermal noise level, and is accompanied
by a shifting fringe-like interference pattern, which limits the detection sensitivity [37,60].
Both solid core and hollow core waveguides (HCWs) have been demonstrated to be very efficient
for mid-IR QCL beam single-mode delivery [61,62]. However solid core fiber operation becomes
multi-mode at wavelength λ > 3 µm and in this range HCWs represent the only solution. In HCWs the
laser beam propagates through an air core by multiple reflections on a metallic inner wall. The main
advantages are a high power threshold, low insertion loss, no-end reflections and low beam divergence
at the waveguide exit. In addition, the waveguide core is coated with a dielectric film with a thickness
suitably chosen to minimize waveguide transmission losses in the metallic layer at the wavelength of
the propagating laser radiation [63].
Recently, Spagnolo et al. have developed a QEPAS sensor system using a HCW coupled single
mode QCL pump source. Single mode laser delivery was obtained using a HCW with inner
silver-silver iodine (Ag-AgI) coatings, an internal bore size of 300 µm, transmission losses of 1 dB/m
and bending losses of 0.1 dB [64]. The basic structure of the fiber is shown in Figure 10.

Figure 10. Simple schematic of the hollow fiber with Ag/AgI coating. Thicknesses are not
drawn to scale.

Protective jacket

Glass capillary
tube

Ag

AgI

Hollow core
Sensors 2014, 14 6184

To fabricate a hollow fiber for mid-IR applications, an Ag layer is deposited inside a glass capillary
tube by flowing a silver solution through the tube. A dielectric layer is then subsequently formed by
flowing an iodine solution through the same tube that reacts with the silver to form AgI. By controlling
the thickness of the AgI dielectric layer, the transmission window of the fiber can be optimized for a
specific wavelength range from 2.5 to 18 µm. The overall loss and spatial mode properties are mainly
determined by the bore size. A single-mode Gaussian-like beam profile output can be obtained when d
<30 λ. However, for practical applications a small bore size is not always desirable, since the smaller
the bore size, the greater the loss, which scales as 1/d3. For laser wavelengths near λ~10 µm, a
300 µm bore fiber offers a good compromise by providing single-mode beam delivery with only a
moderate transmission loss. A fiber coupled QCL-QEPAS system is shown in Figure 11.

Figure 11. A fiber coupled EC-QCL based QEPAS sensor system.

Aspheric Focusing ADM

Lens Gas Flow

EC-QCL
Focuser
Hollow Fiber

The EC-QCL output beam must be mode-matched to optimally couple into the ~0.04 numerical
aperture of the HCW. A ZnSe lens with a 12.7 mm diameter and 40 mm focal length was selected to
ensure a focused spot diameter of <300 µm in order to maximize the laser light delivered by the HWG
to the QTF. A beam waist diameter of ~160 µm was measured in the focal plane of the focusing lens,
which is well below the gap width of the QTF prongs. Hence, 99.4% of the laser light exiting from the
collimator was transmitted through the ADM without touching it and allowing a strong reduction of
the background finger-like pattern in QEPAS spectra [65]. The fiber coupled QCL-QEPAS system was
then tested by employing a 10.54 µm EC-QCL with an output power of up to 90 mW, and choosing
SF6 as the target gas. A SF6 absorption line located at 948.615 cm−1 was selected, which is
interference-free from water interference. For a 1 s lock-in integration time a minimum detection
sensitivity of 50 ppt was achieved , corresponding to a NNEA = 2.7  10−10 cm−1 W Hz−1/2, which
represents a record value for the QEPAS technique [66].

3.5. MOCAM Technique Combined with QEPAS

The modulation cancellation method (MOCAM) is a variation of modulation spectroscopy using

two light sources [67]. The basic concept of MOCAM is that the powers and modulation phases of two
light sources can be adjusted to balance out the background signal, which limits the accuracy of
measurements. In order to perform this technique, the output powers and modulation phases of the two
light sources must be tuned to be in resonance with two selected gas absorption lines, which can be
adjusted so that the signal detected from the reference sample is zero. In this case, the signal from the
analyzed sample will be directly proportional to the deviation of the absorption line strength ratio from
the reference line strength ratio. MOCAM can be used in various implementations that include WM (1f
Sensors 2014, 14 6185

or 2f detection) absorption spectroscopy. For example, the MOCAM technique combined with QEPAS
was successfully used for measurements of temperature differences in a gas mixture [68–71], of isotopic
composition [72,73] and for the detection of broadband absorbers at atmospheric pressure [69–71].

3.5.1. Temperature Measurements and Isotopic Composition of a Gas Mixture

A schematic of the MOCAM-QEPAS architecture for isotopic composition and temperature

measurements is shown in Figure 12.

Figure 12. MOCAM setup for isotope concentration ratios and temperature measurements.
AGS – Analyzed gas sample, RGS – Reference gas sample.

Gas Out Gas In

Sine
Laser 1

AGS
Fiber Splitter Gas Out Gas In

Sine
Laser 2 Attenuation Filter

RGS
Balancing Feedback signal

Two QCLs are wavelength-modulated with the same frequency and the combined emission is
directed to two QEPAS cells, one containing the reference gas sample and the other the analyzed gas
sample. The central wavelength of both lasers must be locked to two selected absorption lines of the
two isotopes gas target (in case of temperature measurements the pair of optical transitions belong to
the same molecular species). The modulation phase and optical power are manually set in such a way
that the QEPAS signals at 2f produced by the two lasers are identical and opposite in phase. The phase
relations are maintained by a phase locked loop. In other words, the two QEPAS signals in the
reference cell can be balanced in such a way that no generation of sound occurs and the QTF detects
no signal with an uncertainty equal to the QTF thermal noise level. For this condition, the signal from
the analyzed sample will be directly proportional to the deviation of the absorption line strength ratio
from the reference ratio in the selected optical configuration.
Spectroscopic temperature measurements are based on the temperature dependence of the absorption
line strength ratio (but independent of pressure) for a pair of optical transitions of the same chemical
species with different lower energy levels. The principle is based on the selection of two spectroscopic
transitions originating at lower states with different energy, can be expressed as follows [68]:

(27)
Sensors 2014, 14 6186

where S1 and S2 are the absorption linestrength of two selected lines, c is the speed of the light, h the
Planck constant and k the Boltzmann constant. The exponential terms contains the difference in lower
state energy ΔE between the two absorption lines accounts for the Boltzmann populations at
temperatures T and T0. In a first approximation for small changes of temperature, R is proportional to:

(28)

Here both E and T are expressed in energy units for simplicity. Thus:

(29)

Since T and ΔE can be assumed approximately constant, the precision in measuring deviation dT of
the analyzed sample temperature from the reference sample temperature is dominated by the error in
measuring dR/R. Assuming that the QEPAS spectrophones are similar and the temperature difference
is small compared to the absolute temperature, it is possible to write:

(30)

where U1 is the signal detected from the analyzed sample when laser 2 (or its modulation) is turned off
and U is the signal detected from the analyzed sample when the signal from the reference cell is zero,
cancelled by balancing the two lasers. The coefficient reflects the fact that the noise of two
spectrophones is uncorrelated and, therefore, adds in quadrature. δ is the deviation from the reference
and can be expressed as:

(31)

where Rst is the ratio in the reference sample. Since the temperature difference between two samples
will be calculated using Equation (29) and ΔR/R is obtained from Equation (30), the temperature
difference is:

(32)

CM is a constant, which include the term T2/ΔE, which depends on the MOCAM configuration and is
determined by an initial setup calibration. The uncertainty δT in the T measurements due to the noise in
the photoacoustic signal δ is given by [67]:

(33)

A C2H2/N2 gas mixture with 0.5% C2H2 concentration was used as a test analyte. The achieved
sensitivity was 30 mK with a lock-in integration time of 17 s [68].
The MOCAM technique combining QEPAS with 2f wavelength modulation was also used to measure
the isotopic 18O/16O ratio in water vapor. The main difference is that in this case two spectral lines
were selected for the two different water isotopes, i.e., H216O and H218O. In particular, the selection of
the isotope absorption lines required that the related lower energy levels were close with the same
quantum numbers, in order to limit the sensitivity of the measurement to temperature variations and to
Sensors 2014, 14 6187

guarantee identical broadening and relaxation properties [72]. The sensitivity reached in measuring the
deviation (expressed in the δ-notation as a deviation from the reference ratio) from a standard sample
δ18O was 1.4‰ for a 200 s lock-in integration time [72,73].

3.5.2. Detection of Broadband, Polyatomic Molecules

Vibrational spectra of most molecules consisting of more than five atoms are dense so that Doppler
and pressure broadening make them unresolved at normal temperature and pressure conditions. As a
result, infrared absorption spectra of such polyatomic molecules consist of broad spectral bands, that
are 100–200 cm−1 wide. Spectroscopic identification of these species requires optical sources with
wide spectral coverage, Thus, QEPAS detection of such molecules requires amplitude modulation of
the laser radiation, which is not recommended for sensitive concentration measurements due to the
presence of a coherent background generated by the scattered and subsequently absorbed light.
However, MOCAM technique combined with QEPAS detection offers an interesting alternative for
sensitive detection of broadband absorbers in the presence of spectrally nonselective background
absorption [69–71]. The schematic of a MOCAM based sensor architecture for broadband molecule
detection is shown in Figure 13.

Figure 13. MOCAM method applied to the detection of broadband absorbers such as
polyatomic molecules and aerosols. AGS – Analyzed gas sample. The signal S will be
proportional to the target gas species concentration ([A]).
Gas Out Gas In

Glan Prism

Laser 1

AGS

Square Wave
Laser 1 Laser 2
Square wave

Laser 2

Wavelength

This approach can be used for the detection of species with broad unresolved absorption features
such as the majority of polyatomic molecules. In this case, one of the lasers is centered on the target
absorption band while the second source is tuned to the background region. When the lasers 1 and 2
are amplitude modulated with 180°phase shift, then the modulation amplitudes can be adjusted so that
there is no signal in the absence of A. If the concentration [A] ≠0, the signal detected at the modulation
Sensors 2014, 14 6188

frequency is proportional to the A concentration. For example, MOCAM has been successfully used
for the detection of hydrazine (N2H4), a highly toxic, unstable, strongly corrosive substance, used in
polymer production, the pharmaceutical industry, and as a rocket fuel. Two independent wide stripe
Fabry-Perot diode lasers were used to detect near-IR absorption of hydrazine vapor, with emission
covering both the tail and the peak of the N2H4 absorption band. Both lasers 1 and 2 emit linearly
polarized light. The polarization plane of one of the lasers was rotated 90° by means of
half-wavelength plate (not shown in Figure 13). The radiation emitted by the two lasers was combined
using the Glan polarizer. The overlapped images of the laser facets were located between the QTF
prongs. No acoustic micro-resonator was used, which reduced the probed optical path to the QTF
thickness, 0.3 mm [69–71]. The MOCAM technique suppressed the background signal level by ~ three
orders of magnitude as compared to unbalanced (one laser) detection. The hydrazine vapor detection
limit was ∼1 ppm with a 1 sec averaging time, corresponding to 4.1 × 10−9 fractional absorption in the
probed 0.3 mm path length. Noise suppression and sensitivity did not improve in the balanced
detection mode and was laser-dominated, ∼100 times higher than the QTF thermal noise limit [69–71].
Wide stripe diode lasers are usually not used for spectroscopic applications because they exhibit
high divergence and multimode (both spatially and spectrally) behavior. Therefore, there is no way to
efficiently couple the radiation from a wide stripe laser into a multipass cell or an optical cavity.
However, this is possible for the QEPAS technique because QTFs are wavelength insensitive
transducers with a short optical path length (~0.2–0.4 mm, i.e., the QTF thickness).

3.6. Quartz-Enhanced Evanescent-Wave PAS

In all PAS system reported so far, open-path cells have been used and precise collimating/focusing
optics or fiber-coupling systems minimize the optical insertion loss and improve the efficiency of
photoacoustic signal generation. An alternative is the use of tapered optical micro/nano fibers to
generate evanescent waves for the photoacoustic generation.
Fiber tapers with diameters down to the sub-wavelength scale and low loss of ~0.2 dB can be
fabricated by using a flame-brushing technique starting from standard single-mode fibers and
controlling the flame movement and fiber stretching rate during processing [74]. The tapered fiber is
threaded through the gap between the two prongs of the QTF, and thus the laser radiation is
guided along the fiber with a very small beam size, hence no precise optical alignment is needed.
Wavelength-modulated light from a single-mode near-IR diode laser is transmitted to the tapered fiber,
and the evanescent field is absorbed by the nearby target gas, generating an acoustic pressure wave that
is detected by the QTF. The quartz-enhanced evanescent-wave PAS configuration is schematically
shown in Figure 14.
With a fiber taper of 1.1 µm waist diameter, a DFB laser with wavelength of 1,532.8 nm and
9.8 mW optical power used as the light source, and a standard QTF (f0 = 32,768 Hz), a minimum
detectable concentration limit of 178 ppm was achieved for C2H2 detection at atmospheric pressure
(with a lock-in integration time of 30 ms), corresponding to a NNEA = 1.96  10−6 cm−1W/Hz1/2 [75].
This detection sensitivity can be further improved by reducing the diameter of the fiber taper and by
using a custom-made QTF optimized for this purpose. Calculations based on finite element method have
shown that as fiber diameter is reduced to <1 µm, the percentage of evanescent field in air increases
Sensors 2014, 14 6189

rapidly. When the diameter of fiber is 0.6 µm, >80% of the light power will be in the evanescent field,
which enables efficient interaction between sensing gas and laser source [76]. This method provides an
alternative to the general open path-based QEPAS, and has the potential advantages of lower insertion
loss, easier optical alignment, and a potentially multiplexed sensing capability.

Figure 14. Schematic of the quartz-enhanced evanescent-wave PAS configuration with a

tapered optical micro fiber. The green circular lines represent the wavefronts of the
acoustic wave.

4. Terahertz QEPAS

4.1. Terahertz Spectroscopy for Gas Sensing

Terahertz (THz) radiation lies in the frequency gap between the infrared and microwaves and has
been studied in various science and engineering fields, such as astronomy and analytical science.
Milestones of THz research include the development of THz time-domain spectroscopy, THz imaging
and THz generation by means of non-linear effects [77,78]. In the last ten years, photonics has led to
the realization and the development of THz QCLs providing compact and stable sources with high
power, continuous-wave operation and single-mode emission. Nanotechnology research has
demonstrated the possibility to use semiconductor nanowire as low-noise and room temperature THz
detectors based on a field-effect transistor configuration, offering an useful alternative to bulky and
costly cryogenic bolometers [79]. Due to recent innovations in photonics and nanotechnology, THz
research can be applied in a wide variety of applications, including information and communications
technology, medical sciences, homeland security, quality and industrial process control [80].
Sensors 2014, 14 6190

Explosives, narcotics and toxic gases have spectral fingerprints and strong absorption bands in the THz
spectral range.
The energy of photons in the THz region allows the study of vibrational activity outside the range of
infrared spectrometers, and rotational and torsional modes of gaseous molecules of higher energy than
those observed by microwave spectrometers. THz QCLs have recently demonstrated good performances in
high-resolution molecular spectroscopy [81–85]. Many gases have absorption strengths that are of the same
order of magnitude as those observed in the mid-IR spectral range and three to six orders of magnitude
stronger than those measured in the microwave region. For example, gas species such as water, nitrogen
compounds, oxygen and chlorine possess strong absorption bands in the THz range and the precise
knowledge of their concentration in the stratosphere and in the upper troposphere is important for the study
and monitoring of chemical processes related to ozone depletion, pollution monitoring and global warming.
THz and sub-THz radiation has long been a valuable tool for astronomers in characterizing astronomical
systems due to the ability of microwave and THz spectra to identify gases by means of their rotational
spectra. High-resolution rotational spectroscopy is also invaluable in providing very precise structural
information regarding molecular species. Rotational spectroscopy is a well-developed and documented
area: extensive libraries of rotational spectra and texts on this subject exist [86].

4.2. Extension of QEPAS Technique in THz Range: Custom-Made Tuning Fork

The QEPAS technique is also an excellent candidate for high performance THz gas spectroscopic
techniques for two reasons: no optical detection is required and the QEPAS signal strongly depends on
the energy relaxation rates of the absorbing gas species. In gas absorption processes that occur in the
THz range, rotational-translation (R-T) relaxation rates are involved, and it was demonstrated that R-T
relaxation rates are up to three orders of magnitude faster with respect to V-T rates commonly
involved in the mid-IR absorption [87]. Thus, the possibility to work with fast relaxing transition
levels allows operating at low gas pressures, and taking advantages of the high QTF Q-factor
enhancing the selectivity of a QEPAS sensor system. The extension of the QEPAS technique to the
THz spectral region was delayed, mainly due to the difficulty of a proper focalization of the THz laser
beam between the prongs of the QTF, since (i) the gap between the prongs is comparable with the
wavelength of the THz radiation and (ii) a THz beam is characterized by a lower spatial radiation
quality. As discussed in previous sections, one of the main issues in mid-infrared QEPAS based sensor
systems is due to the required optimum focusing between the QTF prongs. The laser beam must not
touch the prongs since otherwise an undesirable non-zero background arises due to the laser
contribution. Hence, the use of QTFs with larger prong spacing is mandatory to extend QEPAS
operation in the THz range.
Recently a 4 kHz QTF (T-QTF) having the same geometry as the standard 37.8 KHz, but with a
6 times bigger gap spacing was reported [88,89]. T-QTFs have been realized by using standard
photolithographic technique to etch z-cut quartz wafer. Electrical contacts are designed by depositing
600/2,000 Å chromium/gold layers on both sides of the T-QTF [90]. The T-QTF dimensions are
3.3 cm × 0.4 cm, with a thickness of 0.8 mm; each prong is 17.7 mm long and 1.3 mm wide. The prongs
are separated by a gap of ~800 μm. The schematic of the T-QTF resonator is shown in Figure 15.
Sensors 2014, 14 6191

Figure 15. Schematic of a THz quartz crystal tuning-fork.

By inserting the dimensions of the T-QTF in Equation (12), it is possible to estimate the first two
resonance frequencies related to the two flexural vibrating mode in the vacuum: 4,118 Hz and
25,786 Hz. Resonance frequencies of =4.245 kHz and 25.4 kHz were measured by using the
CEU, at atmospheric pressure, and the corresponding quality factors are: Q1 = 13,100 and Q3 = 9,800.
The discrepancies from the theoretical values can be attributed to four factors: (i) damping effects of
the ambient gas; (ii) additional weight of the electrode gold layers; (iii) dependence of the elasticity
modulus of quartz on the crystallographic axes orientation; and iv) deviations in geometry between the
modeled and the real T-QTF. To study the damping effects induced by the environmental gas the
resonant frequencies and the quality factor dependences as a function of the gas were investigated. As
theoretically predicted in Equation (14), both resonance frequencies have shown a linear dependence
for the gas pressure in the investigated range 10-780 Torr. The Q factor pressure dependence shows an
exponential behavior, as predicted in Equation (17), and rapidly decreases with the gas pressure. The
results obtained from the T-QTF characterization demonstrated that a T-QTF behaves like a near-IR
and mid-IR QTF [89].

Figure 16. Normalized experimental results (dots) of the QEPAS signals as a function of
the vertical position of T-QTF. Data are obtained by detecting 1.55% of methanol in N2 at
10 Torr and by using the experimental setup depicted in Figure 17. The solid line is the
related best fit curve using Equation (3.21).

1.0
Normalized QEPAS signal

0.8

0.6

0.4
14 15 16 17 18
h (mm)
Sensors 2014, 14 6192

Figure 16 shows the dependence of the QEPAS signal as a function of the vertical position of the
laser beam and the best fit obtained by using Equation (25), in order to obtain the vertical position that
maximize the peak value of the THz QEPAS signal. Good agreement between experimental data and
calculation is observed, which confirms the validity of our model.

4.3. THz QEPAS sensor for Methanol Detection

A schematic of the THz QCL-based QEPAS sensor is shown in Figure 17. The THz laser source is a
single-mode CW THz QCL emitting at ~76.3 μm (3.93 THz) [91] mounted on the cold finger of a
continuous-flow cryostat equipped with polymethylpentene (TPX) windows and operating at T = 6 K.
The THz beam was focused between the two prongs of the tuning fork by using two 90° off-axis
paraboloidal gold reflectors. The QTF is housed in a cell with TPX input and output windows. The laser
beam was re-collimated upon exiting the cell by means of a gold parabolic mirror. A reference cell
(15 cm-long) was filled with high concentration of the gas species under study for spectral reference.
Another gold parabolic mirror was used to focus the laser beam exiting the reference cell to a pyroelectric
detector. By means of a pyroelectric camera; a focused beam waist of ~430 µm between the QTF prongs
was measured, which is well below the gap separation of ~800 µm between the QTF prongs.
For a THz-QEPAS spectral scan, the laser frequency can be scanned over 0.025 cm−1 by applying a
low-frequency (10 mHz) voltage ramp up to 1 V to the external analog modulation input of the QCL
current supply. The THz laser output power was ~180 μW. A sinusoidal dither at frequency f1 is
simultaneously added to the low-frequency voltage ramp, to obtain optical frequency modulation of up
to 0.01 cm−1.

Figure 17. Schematic of a THz QEPAS based trace gas sensor. PD – Photodetector.

gas OUT gas IN

2f

3f
Reference
signal
Sensors 2014, 14 6193

The selected methanol absorption line was the rotational translational transition located at
νline = 3.9289 THz (131.054 cm−1) with a line-strength S = 4.28  10−21 cm/mol in HITRAN units [92].
Gas mixtures with different methanol concentrations in pure N2 were obtained by diluting methanol
vapor, collected from a reservoir held at a vapor pressure of 120 Torr at 300 K, with pressurized N2.
For measurements at low concentrations, a certified 100 ppm methanol/N2 gas mixture was used. The
optimal sensor operating conditions were found to occur by using the first resonant frequency f1 of the
T-QTF, at 10 Torr and a modulation amplitude of 600 mV. The linearity and detection sensitivity of
the QEPAS sensor were evaluated by measuring its response to varying methanol concentration in
pure N2. For a 4 s averaging time (and a bandwidth of 0.04169 Hz) a detection sensitivity of 7 ppm,
corresponding to a NNEA of 2.7  10−1 cm−1 W/Hz was obtained [88,89]. This value is comparable
with the best results obtained in the mid-IR spectral range [64–66] and comparable with the detection
sensitivity achieved with cryogenic bolometers.
THz QEPAS detection limit can be further improved by: (i) employing a THz QCL with higher
output power (>100 mW has been reported in [93]); (ii) selecting molecules such as HF, H2S, OH,
NH3, and HCN, having absorption strengths larger than 10−19 cm/mol; and iii) a custom designed
T-QTF of improved geometry in terms of sensing performance.

5. Review of QEPAS-Based Trace Gas Detection

Minimum detection limits can be quantified as the noise equivalent concentration (NEC) or the
minimum detectable absorption coefficient (αmin, in cm−1), allowing different sensors to be compared
without reference to the specific target gas. For estimates of noise and precision, we use the convention
that the noise equivalent concentration (NEC) is the gas target concentration giving a signal equal to
the root mean squared (RMS) value of signal intensity variations (1σ). Although the QTF thermal
noise represents the physical limit for sensor detection, in practice it is not easy to reach such a low
noise level ( ~µVs). Therefore, for many sensor systems, white noise dominates and SNR depends on
the bandwidth Δf, as SNR is Δf −1/2. Furthermore, it is important to also record the value of the
measurement integration time t used to obtain a certain noise limit, and/or to quote limits in units of
normalized noise equivalent absorption coefficient (NNEA) measured in cm−1W/Hz−1/2, by
normalizing the noise equivalent absorption to a 1 Hz measurement bandwidth.
In Table 2 we listed the results obtained so far for QEPAS based gas sensors. For each gas target,
we reported the operating spectral region and pressure, the available laser optical power at the input to
ADM, the type of QEPAS system and the sensor performance in terms of NEC and NNEA.
NNEAs measured to date using QEPAS are better than the best conventional PAS results. A record
NNEA of 2.7  10−10 cm−1W/Hz1/2 is obtained for SF6 detection at a gas pressure of 75 Torr,
employing an external cavity mid-IR QCL fiber coupled to the spectrophone [66]. The sensitivity of
the sensor is a result also of exceptionally large SF6 absorption cross-sections and its fast V-T
relaxation. CO detection in N2 is characterized by a low NNEA (5.3  10−7 cm−1W/Hz1/2) confirming
that the V-T relaxation of the CO fundamental vibration is slow for efficient acoustic generation at
32.7 KHz [29]. A propylene host was found to promote the V-T relaxation of CO leading to an
improvement of the NNEA of ~ one order of magnitude [30]. Similarly, also N2O is characterized by a
slow V-T relaxation and in this case SF6 was added to the gas sample to promote the V-T relaxation
Sensors 2014, 14 6194

leading to a N2O NEC of 7 ppb, for a 1 s lock-in integration time [29]. For CO2 detection, the influence
of the H2O presence as a relaxation promoter in the sample gas mixture was investigated in
considerable detail. Water vapor is known to be an efficient catalyst for the vibrational states. Therefore
increasing the water concentration in gas mixtures involving molecules with slow V-T relaxation rates
increase the detected CO2 QEPAS signal amplitude, up to a 1.5% of H2O concentration, leading to a
minimum detection limit of 18 ppm for a 1 s lock-in integration time [31]. Higher H2O concentrations
result in a lower QEAPS signal, since the relaxation process of CO2 molecules are dominated by
CO2-H2O collisions. Similarly, the QEPAS-based NO detection can be improved by a factor of almost
50 by the addition of H2O with respect to dry NO in N2 [37]. Furthermore, from the results in Table 2
the optimum pressure range to detect molecules with isolated fast-relaxing transitions is ~50–90 Torr.

Table 2. QEPAS detection of trace gases using different QEPAS approaches. IT – signal
integration time.
Molecule Frequency Pressure NNEA Power NEC IT
QEPAS system Ref.
(Target analyte) cm−1 Torr cm−1W/Hz−1/2 mW ppm (s)
NH3 (exhaled air) 6,528.76 90 8·10−9 7 5 On-beam 1 [26]
Ammonia
CO2 (exhaled air) 6,514.25 90 10·10−9 5.2 890 On-beam 1 [26]
Carbon dioxide
H2O (exhaled air) 6,541.29 90 8·10−9 5.2 580 On-beam 1 [26]
Water
NH3 (N2) 6,528.76 60 7.2·10−9 38 0.65 On-beam 1 [27]
Ammonia
H2CO (air) 2,832.48 200 2.2·10−8 3.4 0.55 On-beam 1 [28]
Formaldehyde
N2O (air+5%SF6) 2,195.63 50 1.5·10−8 19 0.007 On-beam 1 [29]
Nitrous oxide
CO (N2) 2,196.66 50 5.3·10−7 13 0.5 On-beam 1 [29]
Carbon monoxide
CO (in propylene) 2,196.66 50 7.4·10−8 6.5 0.14 On-beam 1 [30]
Carbon monoxide
CO2 (air+1. 2%H2O) 4,991.26 50 1.4·10−8 4.4 18 On-beam 1 [31]
Carbon dioxide
HCN (air+50% RH) 6,539.11 60 4.6·10−9 50 0.155 On-beam 1 [32]
Hydrogen cyanide
CO2 (N2+1.5%H2O) 4,991.26 50 1.4·10−8 4.4 18 On-beam 1 [33]
Carbon dioxide
NH3 (N2) 4,986.99 50 8.9·10−9 3.9 3 On-beam 1 [33]
Ammonia
H2O (N2) 7,306.75 60 1.9·10−9 9.5 0.09 On-beam 1 [34]
Water
C2H2 (N2) 6,529.17 75 2.5·10−9 40 0.06 On-beam 1 [34]
Acetylene
CH4 (N2) 6,057.09 950 2.9·10−8 14 2.1 On-beam 1 [35]
Methane
H2CO (N2:75% RH) 2,804.90 75 8.7·10−9 7.2 0.12 On-beam 1 [34]
Formaldehyde
C2H5OH (N2) 1,934.2 770 2.2·10−7 10 90 On-beam 1 [34]
Ethanol
Sensors 2014, 14 6195

Table 2. Cont.
Molecule Frequency Pressure NNEA Power NEC IT
−1 QEPAS system Ref.
(Target analyte) cm Torr −1
cm W/Hz −1/2 mW ppm (s)
C2HF5 (Freon125) 1,208.62 770 7.9·10−9 6.6 0.009 On-beam 1 [25]
Pentafluoroethane
C2H4 (N2) 6,177.07 770 5.4·10−9 15 1.7 On-beam 0.7 [94]
Ethylene
H2O (N2) 7,165.82 770 1.68·10−8 8 9.27 On-beam 1 [36]
Water
NO (N2 humidified) 1,900.08 250 7.5·10−9 100 0.005 On-beam 1 [60
Nitric oxide
NH3 (N2) 6,528.76 575 3.3·10−9 25 0.06 On-beam 10 [38
Ammonia
H2S (N2) 6,357.63 780 5.6·10−9 45 5 On-beam 1 [39]
Hydrogen sulfide
CO2 (N2) 6,321.20 770 4.0·10−9 38 123 On-beam 1 [39]
Carbon dioxide
CH4 (N2+1.2%H2O) 6,057.09 770 3.7·10−9 16 0.24 On-beam 1 [39]
Methane
C2H2 (N2) 6,529.17 770 3.3·10−9 37 0.085 On-beam 1 [40]
Acetylene
NH3 (air humidified) 967.35 130 / 24 0.006 On-beam 1 [41]
Ammonia
CO2 (air humidified) 6,361.25 150 8.2·10−9 45 40 On-beam 1 [41]
Carbon dioxide
NH3 (N2+2.3%H2O) 6,528.76 50 9.1·10−9 50 1.27 On-beam 1 [43]
Ammonia
CH4 (N2+2.3%H2O) 6,057.1 200 2.45·10−8 16 3.2 On-beam 1 [43]
Methane
CO (N2+2.2%H2O) 2,176.28 100 1.48·10−8 71 0.002 On-beam 1 [44]
Carbon monoxide
CO (N2+2.6%H2O) 2,169.2 760 1.61·10−8 400 0.0015 On-beam 1 [45]
Carbon monoxide
N2O (N2+2.6%H2O) 2,169.6 100 2.91·10−9 400 0.023 On-beam 1 [45]
Nitrous oxide
CH4 (N2) 4,245.84 770 / 1.2 1 On-beam 0.1 [46]
Methane
CH4 (N2) 2,958.23 770 4.06·10−9 1 0.1 On-beam 12 [47]
Methane
C2H2 (N2) 6,523.88 720 4.1·10−9 57 0.03 On-beam 1 [48]
Acetylene
HCl (N2) 5,739.26 760 5.2·10−8 15 0.7 On-beam 1 [49]
Hydrochloric acid
Sensors 2014, 14 6196

Table 2. Cont.
Molecule Frequency Pressure NNEA Power NEC IT
−1 QEPAS system Ref.
(Target analyte) cm Torr −1
cm W/Hz −1/2 mW ppm (s)
SO2 (N2+2.4%H2O) 1,380.94 100 2.0·10−8 40 0.1 On-beam 1 [50]
Sulfur dioxide
C2H6 (N2) 2,990.08 150 7.0·10−7 217 0.025 On-beam 3 [95]
Ethane
O2 (N2) 13,099.3 158 4.74·10−7 1228 13 On-beam 1 [96]
Oxygen
H2O (air) 7,161.41 760 6.2·10−9 8 0.26 off-beam 1 [55]
Water
O3 (air) 35,087.7 700 3.0·10−8 0.8 1.27 off-beam 1 [58]
Ozone
SF6 948.62 75 2.7·10−10 18 5·10−5 fiber-coupled 1 [66]
Sulfur hexafluoride
N2H4 (N2) 6,570.00 700 / 62 1 MOCAM 1 [67]
Hydrazine
C2H2 (air) 6,523.88 760 1.96·10−6 9.8 1.58·104 evanescent 1 [75]
Acetylene wave PAS

CH3OH (N2) 131.05 10 2·10−10 0.04 7 bare custom 4 [88]

Methanol QTF

Figure 18. Best NEC results for the gases listed in Table 2 versus employed laser
wavelength, in the UV-Vis, near-IR, mid-IR and THz spectral ranges. The blue, the green
and the red symbols indicate NEC values in the ppm, ppb and ppt concentration ranges,
respectively.

10 ppt
UV-VIS
Noise Equivalent Concentration

Near-IR Mid-IR THz

SF6

100 ppt
1 ppb CO
NO
N2O C2HF5 NH3
10 ppb C2 H 6
HCN
CH4 SO2
100 ppb H2 O
C2 H 2 H2CO

O3 N2H4 HCl
1 ppm C2 H 4
CH3OH
O2 H2 S
10 ppm CO2
C2H5OH
100 ppm
0 2.5 5.0 7.5 10 76.5
Wavelength (μm)
Sensors 2014, 14 6197

In Figure 18 the best noise equivalent concentration are plotted for all investigated gases depicted in
Table 2 as a function of the employed laser wavelength. Since the NEC is related to the laser power
and the absorption linestrength, the best results have been obtained in the mid-IR fingerprint range
where powerful QCLs are available. The low NEC value reported for ethanol [34] is due to large
spectral absorption feature that is a characteristic of this gas and which prevents the use of the efficient
WM QEPAS approach and permits only the use of the AM QEPAS method.

5.1. Long Term Stability of a QEPAS Sensor

Measurements are required to characterize long-term drifts and establish the signal averaging limits,
while the NNEA describes the sensor performance on a short time scale. The approach, described in [97]
introduces the Allan variance of time sequences of measurements to quantify the long-term stability of
optical trace gas sensors. The laser radiation was locked to the absorption line peak while the
absorbing gas concentration and the gas pressure are maintained constant. For these conditions, by
fixing the lock-in amplifier time constant, the lock-in amplifier readings are recorded, by using an
acquisition time at least three-fold the lock-in time constant. The measurements were performed
continuously for several hours. To perform an Allan variance σA analysis, all the data subsets with the
laser targeted onto a specific absorption line have to be stacked together and treated as a single
uninterrupted time sequence. Usually the Allan deviation is shown instead of the variance and
expressed in terms of absorption coefficient or absorbing gas concentration for a particular sensor, thus
allowing to determine the minimum detectable concentration as a function of the lock-in integration
time. The Allan deviation for all time sequences closely follows 1/√t dependence over the
entire duration of the measurements series. This observation verifies that white Johnson noise of the
QTF remains the dominant source of noise even on a multi-hour time scale, and that a QEPAS based
sensor allows unlimited data averaging without base line or sensitivity drift [19,95]. However, for
sensors operating in the field, after some optimum averaging time drift effects can be observed, mostly
due to mechanical movements of different components comprising a QEPAS based sensor system. The
point at which this occurs, and the extent to which performance deteriorates thereafter, are both
application– and installation– specific for a given sensor instrument.

6. Comparison with Existing Optical Techniques and Perspective

When comparing different techniques a figure of merit that makes sense in one application is of
limited value in another, or even difficult to calculate. A possible common metric to compare the
performances of different types of laser based sensors should take into account the available optical
laser power, the strength of the selected absorption line and the integration time used in the
measurements. In this case, the normalized noise equivalent absorption parameter, when it is possible
to compute, represents the best choice. In Figure 19 we compared the performance of several gas
detection techniques in terms of NNEA versus optical pathlength [98,99]. It should be noted that in
most cases the reported NNEA was obtained in a laboratory setting and such performances cannot
easily be replicated in actual field environment. For example, it can be challenging to maintain the
precise alignment needed in sensor systems with long equivalent optical pathlengths.
Sensors 2014, 14 6198

The techniques with the lowest NNEA, i.e., those capable to reach ppb and ppt gas detection
concentrations, are those characterized by very long pathlengths (up to tens of km), namely CDRS,
ICOS and CEAS. However, PAS and in particular QEPAS shows very good performance, reaching
NNEA in the 10−1°cm−1 W/Hz−1/2 range, with the advantage of a much better sensor compactness.

Figure 19. NNEA for categories of gas detection techniques as a function of

optical path-length. Key: BB-CEAS – broadband cavity-enhanced spectroscopy,
CRDS – cavity ring-down spectroscopy, OA-ICOS – off-axis integrated cavity output
spectroscopy, OF-CEAS – optical feedback cavity-enhanced absorption spectroscopy,
NICE-OHMS – noise-immune cavity-enhanced optical heterodyne spectroscopy, PAS
photoacoustic spectroscopy, QEPAS – Quartz-enhanced photoacoustic spectroscopy,
and I-QEPAS – Intracavity quartz-enhanced photoacoustic spectroscopy.
-3
10
BB-CEAS
-5
PAS
10
NNEA (cm-1·W·Hz-1/2)

-7
CRDS
10

OA-
10
-9
ICOS
QEPAS OF-
-11
10 I-QEPAS (?) CEAS
NICE-
-13
OHMS
10
-2 0 2 4
10 10 10 10

Optical pathlength (m)

Three main approaches have to be followed to realize optical sensors with high sensitivity:
(i) selection of optimal molecular transition in terms of absorption strength and absence of possible
interfering gases; (ii) long optical pathlength and/or cavity optical build up; (iii) efficient spectroscopic
detection schemes. Since the QEPAS technique is characterized by direct proportionality between the
signal amplitude and the laser power available for gas excitation, the higher the optical power focused
between the QTF prongs, the lower will be the QEPAS sensor minimum detection limit. Thus, the
possibility to realize intracavity optical build-up and QEPAS detection sensor design may lead to
the realization of an optical sensor system with unprecedented detection sensitivity. Recently a
cavity-enhanced optical feedback-assisted PAS sensor was demonstrated for water vapor detection
reaching a noise-equivalent absorption value of 1.9  10−10 cm−1Hz−1/2 [100]. Furthermore, the
development of an innovative spectroscopic technique, which we called intracavity QEPAS
(I-QEPAS) was reported in [101]. This technique can be considered as a merging of CEAS and
QEPAS for which we estimate an optical resonator enhancement factor of ~250 and an optical
pathlength of 84 m. The I-QEPAS method has been used to detect CO2, reaching a sensitivity of 230
ppt with 10 s averaging time and a corresponding NNEA of 2.5  10−10 Wcm−1/Hz1/2 [101]. Since a
bare QTF was used as an acoustic detection module, further improvement can be expected by adding a
mR system to the ADM. An estimate of the I-QEPAS sensing capability can be obtained by starting
Sensors 2014, 14 6199

from reported QEPAS record sensitivities, i.e. few tens of ppt detection and a corresponding NNEA in
the 10−10 Wcm−1/Hz1/2 range [64–66] and reduce these values by the achieved resonator enhancement
factor (~250). This yields I-QEPAS sensitivities at ppq concentration levels and a corresponding record
low NNEA value in the range 10−0 to 10−12 Wcm−1/Hz1/2, as schematically described in Figure 19.

7. Conclusions

This work has focused on recent advances in the development of quartz-enhanced photoacoustic
trace gas sensors for detection, quantification and monitoring of trace gas species. The current
availability of commercial and research quantum cascade laser sources has allowed the targeting of
strong fundamental rotational-vibrational gas absorption lines in the mid-IR spectral range and pure
rotational lines in the THz range, that are one to two orders of magnitude stronger than overtone
transitions in the near infrared. Progress to-date in terms of spectrophone configuration, performance
optimization and sensitivity for QEPAS sensors was reviewed. The best results in terms of minimum
detectable gas concentration have been obtained by employing acoustic micro-resonator tubes and
positioning a commercial, low cost 32.78 kHz QTF between the tubes to probe the acoustic vibration
excited in the gas contained inside the tubes (on-beam configuration). This configuration increases the
QEPAS sensitivity up to 30 times compared with a QEPAS sensor with a bare QTF and ensures
excellent acoustic isolation from accidental external resonances in the sensor enclosure. Moreover, the
optical alignment is critical, especially with laser sources having limited spatial beam quality. To
overcome these operating limitations three configurations have been developed. In the first approach,
the tuning fork is placed close to a small slit made in the middle of a single resonator tube. The laser
beam does not pass through the QTF prongs since it is located off-beam to acquire the photoacoustic
signal. In the second approach, the laser beam is guided between the two prongs of a bare tuning fork
(without resonator tubes) by using a tapered optical fiber and the associated evanescent-wave effect.
These two approaches partially overcome and minimize the beam quality requirements associated with
the on-beam configuration, but do not reach the same levels of detection sensitivity. The third
approach is based on an optical coupling between the light source and a single-mode hollow core fiber
combined with an on-beam configuration. The design of the source-fiber coupling and output
collimator system achieved a beam waist diameter of ~160 µm between the two QTF prongs, which
simplified the optical alignment considerably. With such a configuration, the QEPAS sensitivity
reached record detectable trace gas concentration levels in part-per-trillion range. QEPAS combined
with a modulation cancellation technique was successfully used for measurements of temperature
differences in a gas mixture, for isotopic measurements and for the detection of spectrally broadband
polyatomic molecules. The recent development of long wavelength quantum cascade lasers made it
feasible to use the QEPAS technique in the THz range by employing a custom-made QTF with a larger
space separation between the two prongs to allow optimized THz radiation beam focusing, thereby
reaching a detection sensitivity level comparable with the best results reported in the mid-IR.
Moreover, an innovative spectroscopic technique, called I-QEPAS (a merging of CEAS and QEPAS
methods) was recently demonstrated and potentially may lead to the realization of sensors with ppq
detection limit and NNEA in the 10−12 Wcm−1/Hz−1/2 range.
Sensors 2014, 14 6200

In conclusion, compact, sensitive and selective QEPAS sensors have been demonstrated to be
effective and mature for numerous real-world applications. These now include different fields such as
environmental monitoring (CO, CO2, CH4, H2CO, C2HF5, N2O, NO2), industrial emission
measurements such as at combustion sites and gas pipelines (HCl, CO2, CH4, CO, NOx, CH2O,), urban
emission coming from automobile traffic (NOx, SOx), rural emission such as horticultural greenhouses
and fruit storage (C2H6, C2H4, CH4, N2O), control for manufacturing processes (SF6, HCl), detection of
medically important molecules (NO, CO, NH3, C2H6, H2S), toxic gases (CH2O, HCl, HCN, N2H4, etc.)
and for planetary science (H2O, CH4,CO, CO2, N2H4, C2H2) and of course environmental monitoring
For example a QEPAS-based sensor was installed in a mobile laboratory to perform atmospheric CH4
and N2O detection near two urban landfill sites located in Houston, TX [102]. The QEPAS sensor
recorded concentration values in very good agreement (<5% difference ) with those measured by the
Aerodyne Research, Inc. “QCL mini monitor” multi-pass optical sensor having a CH4 detection
sensitivity of 300 ppt and N2O detection sensitivity of 60 ppt, both in 1 s [103–105], which
demonstrates the precision, stability and applicability of the QEPAS sensing technique.

Acknowledgements

P. Patimisco and V. Spagnolo acknowledge financial support from three Italian research projects:
PON01 02238, PON02 00675 and PON02 00576. The Rice University group acknowledges financial
support from a National Science Foundation (NSF) ERC MIRTHE award, a NSF-ANR award for
international collaboration in chemistry, “Next generation of Compact Infra-red Laser based Sensor for
Environmental monitoring (NexCILAS).

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