focal point review

LIZHU ZHANG, GUANG TIAN

SCHOOL OF SCIENCE, TIANJIN UNIVERSITY OF TECHNOLOGY AND EDUCATION, TIANJIN
300220, CHINA

JINGSONG LI,* BENLI YU

KEY LABORATORY OF OPTO-ELECTRONIC INFORMATION ACQUISITION AND MANIPULATION
OF MINISTRY OF EDUCATION, ANHUI UNIVERSITY, HEFEI 230601, CHINA

Applications of Absorption Spectroscopy Using

Quantum Cascade Lasers
Infrared laser absorption spectroscopy (LAS) is a promising modern technique for sensing trace gases with high sensitivity, selectivity, and
high time resolution. Mid-infrared quantum cascade lasers, operating in a pulsed or continuous wave mode, have potential as spectroscopic
sources because of their narrow linewidths, single mode operation, tunability, high output power, reliability, low power consumption, and
compactness. This paper reviews some important developments in modern laser absorption spectroscopy based on the use of quantum
cascade laser (QCL) sources. Among the various laser spectroscopic methods, this review is focused on selected absorption spectroscopy
applications of QCLs, with particular emphasis on molecular spectroscopy, industrial process control, combustion diagnostics, and medical
breath analysis.
Index Headings: Laser spectroscopy; Quantum cascade laser; QCL; Spectroscopic applications; Gas analysis.

INTRODUCTION cascade laser (ICL),8 has provided new possibilities for

highly sensitive and selective trace gas sensing utilizing
aser absorption spectroscopy (LAS) is an emerg-

L ing discipline in many fields such as atmospheric

environmental monitoring, industrial process con-
trol, medical diagnostics, and is promising for applica-
tions in which the continuous monitoring of targeted
gases with sensitivity, selectivity, and fast response are
required. Compared with other measurement tech-
niques, LAS has a rapid response, is nondestructive,
and is amenable to remote sensing. Advances in laser
sources and spectroscopic techniques have led to an
increase in the use of LAS for atmospheric and industrial
measurements of trace gases.1–5
Bunsen and Kirchhoff first proposed spectral analysis
in the middle of the 19th century.6 Many important gases
exhibit absorption in the infrared spectral region
(between 0.7 and 25 lm). Near infrared (NIR, between
0.7 and 2.5 lm) spectroscopy techniques have benefited
from developments in telecommunications where inex-
pensive and compact diode laser sources became
available in the 1990s. In contrast, similar lasers were
not available in the middle infrared (MIR, between 2.5
and 25 lm). Recent progress in semiconductor laser
technology, in particular, the advent of the intersubband
quantum cascade laser (QCL)7 and the interband
Received 13 April 2014; accepted 15 June 2014.
* Author to whom correspondence should be sent. E-mail: ljs0625@126.
com.
DOI: 10.1366/14-00001
MIR spectroscopy techniques in combination with mul-
tiple pass cells, modulation techniques, and cavity
enhanced methods. Compared to some traditional MIR
laser sources, QCLs overcome many drawbacks, for
example, the cryogenic cooling requirement and low
power of lead salt diode lasers, the lack of continuous
wavelength tunability, the large size and weight of gas
lasers (e.g., CO and CO2), as well as the complexity of
coherent sources based upon difference frequency
generation (DFG) and optical parametric oscillators
(OPO). Amongst these MIR laser sources, newly devel-
oped QCLs offer the advantages of long lifetime, high
power, compactness, and robustness, which make
instruments based on these laser sources very suited
for long-term in situ and online real-time measurements
of atmospheric trace gases.3 Recently, QCLs have
experienced rapid and dramatic improvements in power,
efficiency, and wavelength range. By carefully designing
the quantum wells, lasing has been achieved at
wavelengths as short as 2.75 lm and as long as 3000 lm
(i.e., 0.1 THz). The longer wavelength devices require
cryogenic cooling still, but room temperature operation
has been observed to at least 16 lm.9–12
In this review, we provide a brief overview of state-of-
the-art QCL techniques in applied laser spectroscopy
and their current applications, beginning with a simple
introduction to the key features of LAS and QCLs, as well
as an overview of the most popular LAS techniques
associated with the fundamental principles. Subsequent-

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focal point review
FIG. 1. Concept of direct absorption spectroscopy.
ly, we focus on several selected applications of QCL-
based modern spectroscopic techniques, in particular,
molecular spectroscopy, industrial process control,
combustion diagnostics, and medical breath analysis.
MODERN LASER SPECTROSCOPY
TECHNIQUES
Direct Absorption Spectroscopy. Direct absorption
spectroscopy (DAS) is a simple, noninvasive, in situ
technique for determining information about gas phase
species, such as quantitative absolute concentration,
temperature, pressure, velocity, and mass flux of the gas
under observation.12–15 However, DAS suffers from a low
sensitivity that limits its extension into several research
fields (e.g., trace gas analysis). The basic principle is
based on the Beer–Lambert law, as shown in Fig. 1.
The transmission of laser light through an absorbing
uniform gaseous substance with an optical path length of
L can be expressed as
Iðv Þ ¼ I0 ðv Þexpð-aðv ÞLÞ ð1Þ
where I(v) and I0(v) is the transmitted and incident light
intensity at frequency of v, respectively, and a(v) = r(v)N0C
is the absorption coefficient of the sample with concentra-
tion of C. The Loschmidt constant N0 is the number density
(molecules per unit volume), which is a function of
temperature T and pressure P. Here, r(v) = /(v - v0)S(T)
is the absorption cross-section of the absorbing species,
S(T) and /(v - v0) are the line strength at temperature T
and the line shape function for the particular absorption
line transition, respectively, v0 is the central frequency of
the absorption line.
Semiconductor diode lasers were first developed in the
mid-1960s16 and found immediate use in DAS for high-
resolution laser spectroscopy commonly referred to as
tunable diode laser absorption spectroscopy (TDLAS).17,18
The wavelength of a diode laser is commonly tuned over a
particular gas absorption line of interest; after traveling
through the sample medium, the laser light intensity is
attenuated and can be measured with a suitable detector.
Therefore, the low sensitivity (detection of absorbance
~10-3) results from the fact that a small light attenuation
has to be measured on top of a large background signal
that in turn is proportional to the intensity of the light
1096 Volume 68, Number 10, 2014
source. As a result, many experimental schemes have
been proposed for improving the sensitivity, generally
classified into two categories; that is, signal enhancement
and noise reduction techniques, for instance, increasing
the absorption path length using multi-pass absorption
cells (e.g., White cell,19 Herriott cell,20 or astigmatic
Herriott cell,21 Chernin cell,22 and integrating sphere23),
and/or combining DAS with suitable modulation tech-
niques and high-finesse optical cavity (discussed in the
next section). From a practical application point of view,
adaptive digital filtering is easy to implement since it
requires no modifications or additions to the apparatus
hardware and can be easily adapted to any experimental
configuration. Mathematical filtering techniques for online
noise reduction or offline data processing of recorded
spectra are a better choice when temporal resolution is
required.24–27
Modulation Spectroscopy. Modulation techniques
are commonly used methods to increase spectral
signal-to-noise ratio (SNR) by reducing the noise
contribution in TDLAS. They make use of the fact that
technical noise usually decreases with increasing
frequency (which is why it is often referred to as 1/f
noise) and improve the SNR by encoding and detecting
the absorption signal at a high frequency, where the
noise level is low. These techniques generally have a
common principle, i.e., they transform the measured
signal into a periodic signal by modulating a certain
parameter, for example, the laser intensity or amplitude,
emission wavelength, or frequency of a laser source,
corresponding to intensity or amplitude modulation,
wavelength modulation, and frequency modulation,
respectively, as well as take advantage of the fact that
a given electric dipole moment of a molecule interacts
with an external electric field.
Amplitude Modulation. The traditional modulation
method for increasing the SNR in laser absorption
spectrometry is to chop (or cut) the laser beam by a
mechanical chopper and to amplify the laser and current
in the detector with a lock-in amplifier. This technique
has some shortcomings due to chopper frequency or
when the background signal is low frequency and
introduces additional mechanical vibration.
Wavelength Modulation Spectroscopy. Currently,
the most common modulation technique is wavelength
 FIG. 2. Schematic diagram of a wavelength modulation spectroscopy system.

modulation spectroscopy (WMS), as depicted in Fig. 2. where Hn(v0,a) is the nth component of the Fourier
Wavelength modulation spectroscopy, also known as series, given by
derivative spectroscopy,28 utilizes modulation frequen- 8 Z p
cies x much smaller than the frequency of the absorption > 1
>
> sðv0 þ a coshÞd h ðn ¼ 0Þ
line of interest. Wavelength modulation spectroscopy < 2p -p
Hn ðv0 ; aÞ ¼ Z
has been used with tunable diode laser sources since >
> 1 p
the early 1970s.29–31 The basic theory of WMS involves a >
:p sðv0 þ a coshÞ  cosðnhÞd h ðn  1Þ
-p
similar idea to DAS, with an additional fast sinusoid (at
frequency f) modulation applied to the laser current. ð5Þ
Traditionally, it performed at kilohertz frequencies, which
is much smaller than the half-width of the absorbing The modulated absorption signal on the photo-detector
feature, usually achieves sensitivities of 10-4 to 10-5 is then processed though a lock-in amplifier that
fractional absorption. The instantaneous laser frequency demodulates the signal at the fundamental modulation
and output laser intensity can be expressed as frequency (first harmonic, 1f) and its integral multiples
(two or higher harmonics), also known as the so-called
v ðt Þ ¼ v0 þ a cosðxt Þ ð2Þ phase sensitive detection. In practical applications, the
second harmonic (i.e., 2f) is commonly utilized in WMS
Iðt Þ ¼ I0 þ i0 cosðxt þ uÞ ð3Þ for improving the spectral signal-to-noise ratio
(SNR).33,34 In the case of optically thin absorption (i.e.,
where a = mDv and i0 are the modulation amplitudes of a(v)CL ,, 1),32 the transmission coefficient can be
laser frequency and intensity modulation, respectively, simplified as s ’ 1 - a(v)L = 1 - /(v - v0)S(T)N0CL.
m is commonly termed the modulation index, Dv is the Therefore, the Fourier coefficient can be further simpli-
half-width at half-maximum of the emission line, while u fied as
is the phase shift between both modulation effects. Z
Depending on the response of the laser source to the SN0 CL p
H2 ðv0 ; aÞ ¼ - /ðv0 þ a coshÞ  cosð2hÞd h ð6Þ
injection current, high-order nonlinear intensity–frequen- p -p
cy modulation effect is possible, which results in the so-
called residual amplitude modulation. This effect is not Therefore, we can see that the amplitude of the 2f
considered in this study. Due to the periodic even signal is linearly proportional to the concentration of the
function characteristic, the time-dependent transmission absorbing species at a given optical path length and
coefficient s(v) can be expanded in a Fourier cosine molecular absorption cross section, assuming that the
series32 laser intensity is constant, i.e.,
X
n¼þ‘ I2f } I0 aCL ð7Þ
sðv0 þ a cosðxt ÞÞ ¼ Hn ðv0 ; aÞcosðnxt Þ ð4Þ
n¼0 Indeed, WMS increases sensitivity by shifting to a

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focal point review
higher frequency detection bandwidth and rejecting
noise (e.g., 1/f laser noise) with lock-in amplifiers.
Wavelength modulation spectroscopy is particularly
useful for probing air-broadened and overlapping ab-
sorption features. Comparing to DAS, this calibration
method removes the need to assign the chosen line(s)
spectroscopically or to measure their integrated line
strengths. The main drawback of WMS is the require-
ment of onsite calibration with a known gas concentra-
tion in some applications where in situ measurements
are desired. This complicates WMS applications in harsh
environments. To overcome this challenge, a calibration-
free WMS has been proposed by several research
groups.34–38
Frequency Modulation Spectroscopy. Frequency
modulation spectroscopy (FMS) is similar to WMS,39–41
but depends on much higher modulation frequencies,
which are comparable to or larger than the half-width of
the absorbing feature, generally between several hun-
dreds of megahertz and gigahertz frequencies. Relevant
information is shifted to radio frequencies, where low-
frequency noise is suppressed. In FMS, modulation
results in the formation of two distinct sidebands shifted
by xm with respect to the carrier x0. In principle, it is a
heterodyne technique and determines the phase shift
imposed on a probe beam by an atomic or molecular line
rather than its typically very weak absorption signal.
Therefore, the line-shapes obtained by FMS are disper-
sive, i.e., with a zero crossing on resonance and a linear
slope, they are ideally suited as a lock signal for laser
frequency stabilization.
Depending on the number of modulation tones, the
methods are referred to as single-tone FMS (i.e.,
standard FM) or two-tone FMS. A key limitation of
standard FM techniques essentially arises from the fact
that, in the presence of pressure broadened lines at
atmospheric pressure environments, high modulation
frequencies are required, and consequently the detec-
tion and processing electronics must have wide band-
widths. The two-tone technique combines the
advantages of standard FM with the benefits of a
considerable reduction in detection bandwidth, with an
additional improvement in signal-to-noise ratio.42–44 This
technique was first proposed in 1982 for a tunable diode
laser with small modulation frequencies.45 In 1986, it was
extended to much higher frequencies (up to 16 GHz)46
using a continuous wave (CW) dye laser source and an
electro-optic modulator. Subsequently, high frequency
single-tone and two-tone FM with a lead-salt diode laser
was achieved,47 thus demonstrating the general validity
of these techniques, offering the possibility of quantum
noise limited detection so that laser source and detector
limited sensitivities of the order of 10-7 to 10-8 are
possible.48,49 Finally, it is worth noting that the two-tone
FM signal is proportional to the square of the FM index
rather than to the FM index as in conventional single-
tone FMS, and no phase information is encoded.
In 2006 and 2005, Gagliardi et al.50–52 investigated the
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performance of QCLs at around 8.1 and 7.3 lm
wavelength using single-tone and two-tone techniques
for high-frequency modulation spectroscopy on low-
pressure N2O and CH4 gases, respectively. Although
some difficulties are encountered, they finally concluded
that QCLs are suitable for this kind of spectroscopy in the
mid-infrared region. Related technologies of tunable
diode laser-based WMS, FMS, and two-tone FMS and
their applications have been reviewed by Song and
Jung.53 Therefore, they will not be addressed in this
paper.
Magnetic Rotation Modulation Spectroscopy. An-
other promising technique is the so-called magnetic
rotation modulation spectroscopy, namely, the modula-
tion of the absorption coefficient of a specific absorption
line by means of the Zeeman, Stark, and Faraday effect
using an external magnetic field (Fig. 3). Magnetic
rotation spectroscopy was first reported in the 1980s54
and takes advantage of the fact that a given electric
dipole moment of a molecule interacts with an external
electric field because many important molecules such as
ammonia, nitric acid and nitric oxide, formaldehyde,
hydrogen peroxide, hydrogen fluoride, oxygen, OH
radicals, and others show a permanent electric dipole
moment,55 which is a prerequisite for interaction with an
external electric field. This interaction causes a splitting
and shift of the energy levels of the sample molecule.
This enhances the specificity of detection of certain
gases because it minimizes the effect of interfering
absorbing species that have no electric dipole moment,
such as water vapor.
In 1984, Sasada56 reported that several combination
band transitions for NH3 are observed by Stark modula-
tion spectroscopy with a 1.23 lm semiconductor laser. In
1995, Smith et al.57 demonstrated frequency modulation-
enhanced magnetic rotation spectroscopy for detecting
local concentrations of gaseous NO2, and a detection
limit of 20 ppbv (parts per billion by volume) was
achieved. Two years later, Brecha et al.58 presented
the results of a study of molecular oxygen by magnetic
rotation spectroscopy based on the use of a semicon-
ductor diode laser operating near room temperature at
762 nm. In 2009, Sabana et al.59 employed a Faraday
modulation spectroscopy technique based on a CW
distributed feedback QCL operating near 5.4 lm for
simultaneous detection of 14NO and 15NO. The detection
limit (1r) of 6 ppb/=Hz for 15NO and 62 ppb/=Hz for
14
NO was achieved. The isotope ratio (d15N) was
determined with a precision (1r) of 0.52% at 800 s
averaging time for 100 parts per million (ppm) NO gas
with a time resolution of 2 s. In 2011, a Faraday
modulation spectrometer for sensitive and fast NO
detection at 5.33 lm utilizing a room temperature
continuous wave distributed feedback QCL was reported
by Kluczynski et al.60 The spectrometer provided a
detection limit of 4.5 ppb for a response time of 1 s.
Moreover, most related work on the use of diode laser
(VCSEL and QCL) based Faraday rotation spectroscopy
 FIG. 3. Block diagram of a magnetic rotation modulation spectroscopy system.

for trace gases sensing (O2, NO, and OH radicals) was
carried out by the Wysocki’s group at Princeton
University.61–63
High-Finesse Optical Cavity Enhanced Spectrosco-
py. The high-finesse optical cavity enhanced spectros-
copy technique, which takes advantage of long optical
path length absorption in high-finesse optical cavities, is
based on the observation of the decay rate of an injected
laser beam stored in a cavity composed of ultrahigh
reflective and low-loss dielectric mirrors. High-finesse
optical cavities allow a large amount of light energy to
build up in the cavity. The low-loss dielectric mirrors
allow light to leak out of the optical cavity to characterize
the absorption of gas inside the cavity. These kinds of
cavity-based methods are generally classified into cavity
ring-down spectroscopy (CRDS), and its variants such as
cavity enhanced absorption spectroscopy (CEAS) and
integrated cavity output spectroscopy (ICOS).
Cavity ring-down spectroscopy is also a direct
absorption technique, which can be performed with
pulsed or continuous light sources and has a signifi-
cantly higher sensitivity than conventional absorption
spectroscopy. The so-called CRDS technique was first
experimentally demonstrated by O’Keefe and Deacon in
1988.64 This technique is based on the observation of the
decay rate of an injected laser beam stored in a closed
optical cavity composed of ultrahigh reflective spherical
mirrors, as shown in Fig. 4. The advantage over
traditional absorption spectroscopy results from the
intrinsic insensitivity to light source intensity fluctuations

FIG. 4. Scheme of the experimental setup for CRDS.

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focal point review
FIG. 5. Schematic diagram of the traditional photoacoustic spectroscopy system.
and the extremely long effective path lengths (many
kilometers) that can be realized in short optical cavities
(tens of centimeters). The sensitivity of CRDS is
ultimately limited by the accuracy of the decay time
measurement. Ten years later, two modifications of the
CRDS technique, ICOS and CEAS, were proposed
independently in 1998 by O’Keefe65 and Engeln et al.66
The concept of the three methods is similar, but there is
a difference related to the alignment of a laser beam and
the cavity as well as to the mode structure. One big
advantage of ICOS and CEAS as compared with CRDS is
that it can be used without limitations concerning ring-
down time or mode matching between the laser
frequency and the cavity free spectral range (FSR).
Furthermore, the most promising approach to merge
CEAS with the frequency modulation technique was
obtained close to shot noise sensitivity of 1 3 10-14 cm-1
by Ye et al.67 and is known as noise-immune cavity-
enhanced optical-heterodyne molecular spectroscopy
(NICE-OHMS). This sensitivity is superior to that
achieved with CRDS, but the technical requirements
are stringent. During the last decades, research on
various CRDS detection schemes has been widely
explored, as recently described in several review
publications.68–70
Photoacoustic Spectroscopy. Photoacoustic spec-
troscopy (PAS) originates from the discovery of photo-
acoustic (PA) or optoacoustic effect by Bell in 1880.71 He
found that when a beam of sunlight rapidly interrupted
with a rotating slotted disk was focused onto thin
diaphragms, sound was emitted. The absorbed energy
from the light is transformed into kinetic energy of the
sample by energy exchange processes. This results in
local heating and the creation of a pressure wave or
sound. A PA spectrum of a sample can be recorded by
measuring the sound at different wavelengths. Photo-
acoustic spectroscopy can be applied to solids, liquids,
and gases and is only sensitive to sample absorption,
not scattering losses.
Photoacoustic spectroscopy is a very promising
technique for trace gaseous species detection. In the
traditional PAS experiment (as shown in Fig. 5), sample
materials in or sampled into a closed cell are irradiated
1100 Volume 68, Number 10, 2014
using either a pulsed or a wavelength- or amplitude-
modulated light source. The sample species absorb the
light and are thermally excited, causing expansion and
contraction of the gas within the cell in synchronization
with the modulation frequency or laser pulse repetition
frequency. The resulting dynamic motion of the gas
creates an acoustic pressure front that can be monitored
by a microphone or a piezoelectric crystal. The PA signal
S in volts can be described as
S ¼ Sm PCcell Ntot cm r ð8Þ
where the microphone sensitivity Sm is in units of
millivolts per pascal; the optical power of light radiation
source P is in watts; the PA cell response constant Ccell
has units of pascal per inverse centimeters per watt; Ntot
is the total number density of molecules (molecule/cm3);
and coefficients cm and r are the concentration and
absorption cross-section of the analyte, respectively.
The PA cell constant Ccell is a scaling factor depending
on the PA cell geometry, on the modulation frequency,
and on the measurement conditions. It usually can be
determined experimentally from measurements with
known gas absorption and certified concentration. On
the other hand, we can see that PAS is a laser power
dependent technique.
Photoacoustic spectroscopy as a calorimetric spec-
troscopy technique has gradually matured in utility with
significant performance improvements in light sources
and modulators and in PA signal transducers. This
technique has the potential for compact, robust, highly
selective, highly sensitive, large dynamic range, and
relatively low-cost trace gas analysis. Furthermore,
because the acoustic properties of the PA system (e.g.,
microphone responses) do not depend on the spectral
distribution of the absorbed radiation, PA spectrometers
are optically broadband devices; that is, wavelength
independent.
From the technique point of view, several promising
methods of improving the sensitivity of PAS have been
proposed, for instance, acoustic cell resonant photo-
acoustic spectroscopy (R-PAS),72–76 wavelength modu-
lation photoacoustic spectroscopy (WM-PAS),77–80 multi-
pass enhanced photoacoustic spectroscopy (ME-
PAS),81,82 cavity-enhanced photoacoustic spectroscopy
(CE-PAS).83,84 Since the early 2000s, significant devel-
opment and improvement has occurred to the sensing
element. Novel sensing methods for PAS have been
proposed, such as quartz-enhanced photoacoustic spec-
troscopy (QEPAS)85–88 and cantilever-enhanced photo-
acoustic spectroscopy (CEPAS).89–94 For an in-depth
review of PAS techniques, the reader is referred to
other publications.95–97 A comprehensive review of the
recent development and progress of infrared PAS
techniques to 2011 was reported by Li et al.98
SELECTED APPLICATIONS OF QUANTUM
CASCADE LASER-BASED SPECTROSCOPY
TECHNIQUES
Molecular Spectroscopy. Molecular spectroscopic
parameters are the essential elements needed in laser
absorption spectroscopy techniques. Especially for
direct absorption techniques, highly accurate trace gas
concentration measurements rely on the molecular
absorption line intensity. For atmospheric applications,
therefore, a good knowledge of line parameters (i.e.,
positions, strengths, pressure-broadening, and shift
coefficients) of the spectral lines is required to very
high precision and accuracy.
Important work on developing a QCL absorption
spectrometer for MIR molecular spectroscopy study was
carried out by the Groupe de Spectrométrie Moléculaire
et Atmosphérique (GSMA) of Reims University (France).
Water vapor in the atmosphere is an important green-
house gas and is thereby a key component of Earth’s
climate system. Most terrestrial water vapor is located in
the troposphere. A better understanding of the mecha-
nisms involved in the injection of tropical tropospheric
H2O is of importance. The measurement of water vapor
isotopes can be helpful to address this issue. Therefore,
the GSMA reported a laboratory study of H216O, H218O,
and HDO line intensities between 1483 to 1487 cm-1,99
which is suitable for in situ laser sensing of these
isotopologues in the atmosphere using a continuous
wave distributed feedback quantum cascade laser (CW-
DFB-QCL) near 6.7 lm. Line intensities and self-broad-
ening coefficients were measured in the m1 band of SO2
and 34SO2, as well as m1 þ m2–m2 bands of 32SO2 with a CW-
DFB-QCL at 9.1 lm between 1088 and 1090 cm-1.100,101
Furthermore, five lines of the m1 band of N2O at 7.9 lm
(spectral region ranging from 1275 to 1280 cm-1) have
been studied.102 The results of intensity measurements,
air-broadening coefficients, and their variation in temper-
ature from -58 8C up to ambient temperature are
compared with previous determinations and available
databases.
Recently, McCall et al.103,104 observed the v8 vibrational
band of methylene bromide (CH2Br2) and the v2 bending
region of D2O using a QCL-based cavity ring-down
spectrometer. A supersonic free-jet spectrum of the m4
band of CF3Cl from 1215.8 to 1220.6 cm-1 was measured
using a liquid nitrogen cooled QCL and a 2.8 m White cell.105
In addition, Tonokura et al.106,107 demonstrated the spectral
line parameters (line strength and N2-broadening coeffi-
cients) measurements of the v3 band of hydroperoxyl (HO2)
radical in the mid-infrared region at around 1065 cm-1
using CW-DFB-QCL spectroscopy. Two of the strongest
formaldehyde (H2CO) m6 band transitions around 8 lm are
assigned as (1, 1, 1) (2, 0, 2) and (10, 1, 9) (9, 2, 8)
centered at 1252.11231 and 1253.14392 cm-1 by Wang and
Sharples.108 Pressure-induced broadening and shift coef-
ficients for these transitions with a variety of gases (He, Ne,
Kr, Ar, N2,O2, and CO2) was also determined using pulsed
DFB-QCL-based absorption spectroscopy. Lee et al.109
determined the effective line strengths of the trans
conformer of nitrous acid (HONO) near 1275 cm-1 and of
the cis conformer at 1660 cm-1, both at a spectral resolution
of 0.001 cm-1 by utilizing CW-QCL-based differential
absorption spectroscopy.
The strong m2 vibrational band of ammonia (NH3)
between 9–12 lm has a high absorption strength needed
for sensing trace concentrations. Within this band, the
1103.46 cm-1 feature is one of the strongest and has
minimal interference from CO2 and H2O. However, the
six rotational transitions that make up this feature have
not been studied previously with absorption spectrosco-
py due to their small line spacing ranging from 0.004 to
0.029 cm-1. A tunable CW-QCL was used to accurately
study these six NH3 transitions between 1100.4 and
1108.2 cm-1 by Owen et al.110 Most recently, the state of
the art of high resolution terahertz spectroscopy with
QCLs was reviewed by Hübers et al.111
Industrial Process Control and Combustion Diag-
nostics. The High Temperature Gas Dynamics Labora-
tory at Stanford University has been active in combustion
diagnostics for over 40 years. This group has published
over 400 scientific papers, dealing with advances in
shockwave physics and chemistry, laser spectroscopy,
advanced optical diagnostics and sensors, as well as
chemical kinetics, combustion science, and advanced
propulsion. Nitric oxide (NO) is an important atmospheric
constituent of the oxides of nitrogen (NOx), and the
majority of this pollutant is formed from the combustion
of fossil fuels. As a result, the electric-power industry
has a growing need to develop reliable control systems
to suppress the release of NOx effluent from combustion-
driven generation of electricity. Nitric oxide has transi-
tions in three different vibrational bands, two overtone
bands v3 and v2 near 1.8 and 2.7 lm, respectively, and
the fundamental band v1 near 5.2 lm. The fundamental
band holds the most promising candidate transitions in
terms of their strong absorption (about 100 times
stronger line strengths than in the first overtone band)
and relatively weaker interference transitions of the
other combustion species. In 2011, a novel external
cavity (EC)-QCL-based MIR absorption sensor for in situ
detection of NO in combustion exhaust gases was
developed and demonstrated for temperatures up to
700 K.112 A NO detection limit of ,60 ppb m (Hz)-1/2 was
APPLIED SPECTROSCOPY OA 1101
focal point review
obtained with a laboratory combustion exhaust rig and a
1.79 m constant temperature, line-of-sight path. The
sensor system was modified with calibration-free WMS
(i.e., 1f-normalized WMS with second-harmonic detection
strategy, WMS-2f/1f) for improving the sensor perfor-
mance. A 0.3 ppm-m detection limit was estimated using
the R15.5 transition near 1927 cm-1 with 1 s averaging.113
Another key feature of DAS and WMS is the capacity
for temperature measurements by using the ratio of
absorption peaks or line shape integrated absorption of
two neighboring molecular absorption lines. Carbon
monoxide (CO) is also a typical pollutant resulting from
the incomplete combustion of carbon-based fuels that
are widely used for power generation, industrial heating,
petrochemical refining, and propulsion. The strongest
absorption of the CO fundamental band is at ~4.6 lm,
providing orders-of-magnitude greater sensitivity than
the overtone bands accessible with telecommunications
lasers. A high-speed (up to 1–2 kHz) scanned-wave-
length absorption sensor utilizing a thermoelectrically
cooled CW-QCL source and both WMS and DAS
techniques for CO detection at 4.6 lm and high-
temperature thermometry between from 900 to 4000 K
was developed.114,115 The high-temperature measure-
ments of CO mole fraction and temperature agreed with
the post-reflected shock conditions within 61.5 and
61.2% for DAS (or 61.9% for WMS), respectively. A
method for measuring the temporal temperature and
number density in a rapid compression machine (RCM)
using QCL absorption spectroscopy near 7.6 lm was
developed by the Sung group.116,117 The ratios of H2O
absorption peaks at 1316.55 and 1316.97 cm-1 were used
for measurements. For RCM temperatures between 1000
and 1200 K and pressures between 10 and 20 bars, the
measured temperature was found to be within 65 K of
the calculated values. For the measured temporal
number density of H2O, an accuracy of 1% was obtained.
Hübner et al.118 reported gas temperature measurements
(ranging from about 300 K up to about 500 K) in a pulsed DC
air plasma admixed with 0.8% NO at 1900 cm-1 (5.26 lm)
using pulsed quantum cascade laser absorption spectros-
copy (QCLAS) with a pulse repetition frequency of 30 kHz,
leading to a time resolution of 33 ls.
Plasma diagnostics were reported by researchers at
the Leibniz Institute for Plasma Science and Technology
(IPN) Greifswald (Germany). The recent development of
quantum cascade lasers (QCLs) for the monitoring and
control of industrial plasma processes were summarized
successively by Röpcke et al.119–122 at IPN. The current
state-of-the-art terahertz QCL technology and applica-
tions focusing on plasma diagnostics was reported in the
work of Mahler et al.123 Most recently, Yumii et al.124
demonstrated NO2 concentration or density measure-
ments in a small plasma of a nitrogen oxide (NOx)
treatment reactor using sensitive QCL absorption spec-
troscopy. The high sensitivity of spectroscopy is
achieved by the amplitude-to-time conversion technique,
and the observation is consistent with that of an earlier
1102 Volume 68, Number 10, 2014
study on NO decomposition by the same type of plasma
reactor.125
Medical Breath Analysis. Among the numerous
applications of QCL trace gas sensors, the analysis of
human breath for (early) diagnosis of diseases has one
of the highest potential impacts on public health and
quality of life. In clinical medicine (such as in critical care
and operating room settings), breath gas analysis is a
promising new field of medicine and medical instrumen-
tation. Potentially, breath gas analysis can offer nonin-
vasive, real-time, and point-of-care disease diagnostics
and metabolic status monitoring with minimal risk and
negligible discomfort for patients. Employing QCL-based
spectroscopy technologies to perform concentration
measurements of different molecular species in breath
gas were reported by the Laser Spectroscopy and
Sensing Lab at ETH Zurich led by Markus Sigrist, the
Life Science Trace Gas Research Group at Radboud
University led by Frans Harren, and the Laser Science
Group at Rice University led by Frank Tittel. The
research activities of the Sigrist group focused on
fundamental aspects and applications in monitoring
and analysis of trace gases (from atmospheric chemis-
try, industrial process surveillance, agriculture to med-
ical diagnostics) by employing laser spectroscopic
techniques, such as PAS and CRDS. New research
areas concerning noninvasive glucose detection in
human tissue and the analysis of drugs in saliva have
recently been carried out by this group.126,127 The Harren
group focused on trace detection of gases of interest in
plant physiology, post-harvest research, soil science,
microbiology, ecology, molecular biology, medicine, and
human health involving DAS with multi-pass cell, WMS
and FMS, PAS, CRDS, CEAS and ICOS, NICE-OHMS, as
well as FRS. These applications include such gases as
C2H4, C2H6, CH4, NO, CO, CO2, water vapor, aldehydes,
alcohols, ketones, acids, terpenoids, and many other
hydrocarbons, all at or below the parts per billion by
volume concentration level. This work was summarized
in Refs. 128–134. The research at Tittel’s group focused
on the further development of advanced mid-infrared
trace gas sensors for applications in four technical
areas: environmental monitoring, medical diagnostics,
and the life sciences, industrial process analysis and
control, as well as nuclear security. This research will
take advantage of recent, significant advances in the
commercial availability of high performance mid-infra-
red QCL and interband cascade laser (ICL) devices in the
3 to 11 lm spectral range and current laser spectroscopy
techniques, such as QEPAS, ICOS, and CRDS. The
recent trends and developments of laser-spectroscopy-
based techniques for applications in breath analysis to
2006 and to 2010 was successively presented by this
group.135–137 Considering ammonia (NH3) inherent reac-
tivity, factors influencing breath ammonia determination
in both breath instrumentation and the breath collection
process were investigated by their collaborator.138
Additional review articles on this topic from other groups
can be found in Refs. 139–145. Here, we will review
recent developments in laser spectroscopy for breath
gas analysis utilizing novel QCL-laser sources, which
are not summarized in previous reviews.
Recent studies show that numerous diseases are
associated with oxidative stress, e.g., atherosclerosis,
Parkinson’s, Alzheimer’s, and different inflammations of
the respiratory tract. Carbon monoxide (CO) in human
breath is another focus of research because of the
potential use of CO as a biomarker molecule for the
abovementioned diseases. The researchers at the
Institut für Lasermedizin (Germany) reported the online
analysis of exhaled CO using a cavity leak-out spectros-
copy system. A time resolution of less than 1 s and a
detection limit of 7 ppb Hz-1/2 were obtained,146 and
different spectroscopic techniques for CO quantifications
were compared.147 In 2011, Rubin et al.148 used a pulsed
DFB-QCL in the spectral region around 2300 cm-1 in a
flow-through system for 12CO2/13CO2 isotope ratio deter-
mination in human breath. The analysis was based on a
Lorentzian fit of single rotational-vibrational lines for
12
CO2 and 13CO2 within a spectral window of 2 cm-1
providing parts per billion sensitivity for the determina-
tion of the absolute 13CO2 concentration. Most recently,
Wörle et al.149 demonstrated an EC-QCL (operating in the
spectral range from 2150 to 2450 cm-1) with a miniatur-
ized hollow waveguide gas cell for quantitatively
determining the 12CO2/13CO2 ratio in the exhaled breath
of mice. Highly accurate determinations of the isotope
ratio in breath samples collected from a mouse research
unit validated via hyphenated gas chromatography-mass
spectrometry, which confirmed the viability of the EC-
QCL sensing technique for isotope-selective exhaled
breath analysis. In addition, acetone at sub-ppm levels
was reported by Ciaffoni et al.150 in a breath sample with
a precision of 0.17 ppm (1r) by combining a CW-DFB-
QCL operating at 8.2 lm with sensitive CEAS.
Laser absorption spectroscopy is widely recognized
for applications where continuous monitoring of targeted
exhaled gases with sensitivity, selectivity, and fast
response are required, such as in critical care and
operating room settings. Currently, a number of bio-
marker molecules have been identified in human breath
gas that could be used to predict disease and disease
progression. Single-molecule exhaled breath LAS sen-
sors are commercially available. For example, an
exhaled nitric oxide sensor (Breathmeter) is available
from Ekips Technologies, Inc., and an exhaled ammonia
sensor (Nephrolux) is available from Pranalytica, Inc.
The availability of real-time, portable monitors will
represent a breakthrough for clinical diagnosis.
CONCLUSIONS AND OUTLOOK
The aim of this paper was to review recent develop-
ments and applications of laser absorption spectroscop-
ic techniques utilizing novel QCLs as light sources, with
particular emphasis on molecular spectroscopy, indus-
trial process control, combustion diagnostics, and
medical breath analysis. Quantum-cascade-laser-based
gas analyzers are usually for online and real-time gas
concentration monitoring and offer many benefits over
conventional sensors, such as low-power consumption,
high specificity, high sensitivity, fast response, and
provide enough accuracy and precision to fulfill different
performance requirements. The current challenge is to
extend the capabilities of QCLs toward longer wave-
lengths to cover the far infrared and terahertz regions of
the spectrum and the realization of their operation at
room temperature. We can expect that QCL-based
sensors will enable new science and will lead to many
exciting discoveries in molecular physics as well as in
astronomy and planetary physics.
ACKNOWLEDGMENTS
The authors are grateful for the financial support from Tianjin
Application Fundamental and Frontier Technology Research projects
(Grant No. 14JCYBJC17100) and Anhui University Personnel Recruiting
Project of Academic and Technical Leaders (Grant No. 10117700014).
The authors gratefully acknowledge the anonymous reviewers and the
editor for their valuable comments and suggestions to improve the
quality of the paper.
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