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Air Quality Monitoring with

Photoacoustic Spectroscopy
Tunable, narrow bandwidth mid-IR laser sources for compact trace gas analysis sys-
tems with ppb sensitivity
Håkan Karlsson and Sauli Sinisalo

The ultimate instrumentation for trace

gas analysis and detection in air qual- Gas exchange and Optical microphone
ity monitoring as well as industrial temperature controller digital signal
process control would be one that can Gas exchange processor unit
simultaneously provide a sensitive, unit and pump
selective, and fast, multi-gas measure- Readout interferometer
ment with wide dynamic range all in a Sample
compact and robust system. One of the out Cantilever Laser beam
few such promising technologies that
can deliver these requirements is l­aser Sample
based photoacoustic spectroscopy in
(PAS). In this article, the PAS tech-
nique is presented using the Cobolt Beam
External
Odin tunable mid-IR laser. dump Gas
valves laser source

In PAS, the rotational and vibrational Photoacoustic cell Balance cell

states of molecules are excited with in- PA201 Detector Cover
frared light pulses and the absorbed
energy translates into kinetic energy
Fig. 1  Schematics of a modern cantilever-enhanced photoacoustic (CE-PAS) detector
pulses, which form an acoustic wave
that can be detected with a microphone
[1]. Due to the nature of the direct ab- sible to achieve orders of magnitude ideal choice for driving CA-PAS instru-
sorption detection method of the pho- enhancement in the sensitivity and the ments. OPO is a non-linear optical de-
toacoustic effect, the instrument does dynamic range compared to with con- vice that down-converts the wavelength
not require long absorption path lengths denser microphones [2, 3]. Additionally, from a pump laser into two longer
and the background drift is virtually the silicon cantilever withstands rela- wavelengths in an optical resonator.
zero. This comes from the fact, that tively high flow rates and external stress The emission wavelengths depend
when no target molecules are present, without stretching or breaking. on the configuration of the nonlinear
no signal is detected [1, 2]. The photo- Thanks to recent development in optical crystal (NLO) and the accessi-
acoustic effect was already discovered by technologies for mid-IR light sources, ble wavelength span is ultimately lim-
Alexander Graham Bell in 1880, but the it is now possible to run cantilever en- ited only by the transmission window
sensitivity of the method was quite lim- hanced (CE)-PAS instruments with of the NLO. This very broad spectral
ited by the insensitive microphone tech- monochromatic and tunable wave- selectivity and tuning capability is a
nology until the late 20th Century. Now, lengths, broad spectral selectivity and general advantage of OPOs over other
with the current state-of-the art MEMS high output powers. The joint use of mid-IR light sources. More specifically,
fabricated cantilever microphones with these technologies brings a new level OPOs can provide high output powers
optical laser readout, it has been pos- in sensitivity and selectivity with be- and freely selectable wavelengths in
low ppb (parts per billion) sensitivity the 2.8 – 3.6 μm range which is an es-
[4]. There are a number of laser tech- pecially important wavelength range
nologies now available on the market for sensitive hydrocarbon detection as
ωpump capable of providing spectrally flexible it encompasses some of the strongest
ωsignal
narrow-band emission in the mid IR fundamental molecular transitions of
ωidler spectral range; quantum cascade ­lasers several pollutive or poisonous indus-
ΛQPM
ωpump+ ωsignal+ ωidler (QCLs), inter-band cascade lasers trial chemicals such as BTX, C2H2, CH4,
(ICLs), DFB diode lasers and optical HCN, HCL, HF, etc.
Fig. 2  Schematics of signal-resonant OPO based on QPM non- parametric oscillators (OPOs). In many This wavelength region is not readily
linear optical crystal aspects, the OPO technology is the most reachable with QCL’s and the available

36  Optik&Photonik 1/2017  © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Spectroscopy

1
narrowband Odin
0.9 standard Odin
1
0.8
0.8 0.7
Amplitude (a.u.)

Amplitude (a.u.)
0.6
0.6
0.5

0.4 0.4
0.3
0.2 0.2
0.1
0
3400 3410 3420 3430 3440 3450 3460 3470 0
3426 3428 3430 3432 3434 3436
Wavelength (nm) Wavelength (nm)

Fig. 3 Continuous spectral tuning of the Cobolt Odin over 60 nm (a), typical line width (b)

power levels of DFBs and ICLs in this re- emission. The OPO is pumped with a ambient conditions (e.g. resistant to
gion are orders of magnitude lower than high repetition rate 1064 nm laser and 60 g shocks and exposure to -20 °C to
those of OPOs and not sufficient for ex- resonant for the signal wavelength re- +70 °C cycling), bringing the OPO tech-
treme sensitivity. Moreover, the broad sulting in up to 100 mW output power nology to a new scale of size, reliability
tuning capability of OPO compared to in the idler wavelength. The QPM crys- and easy-of-use that enables integration
other mid-IR technologies allows for tal can be engineered for emission any- into compact instrumentation for in-
multi-gas detection of several compo- where between 2 – 5 μm and tailored for field trace gas detection.
nents with common signal processing narrow-band (1 nm standard, < 0.2 nm The numerous promising applica-
and chemometrics. The main drawback custom) emission. The emission line tions for the compact OPO/CE-PAS
of the OPO technology has traditionally can also be continuously tuned over technology include for instance the
been the bulkiness and complexity of > 60 nm. environmental monitoring of methane
available sources. However, recent ad- Both the pump laser and the OPO (CH4), ethanol monitoring for automo-
vancements in OPO designs and laser resonator are assembled into a sin- tive evaporative measurement and the
packaging technology have enabled gle hermetically sealed package using multi-component analysis of BTX for
development of a new class of OPO de- the company’s proprietary HTCure industrial emissions monitoring and
vices of significantly smaller size. technology for compact and robust la- process control. In these applications,
The Cobolt Odin is based on a peri- ser assembly. The all-integrated laser the OPO / CE-PAS technology has a
odically poled NLO for ultimately wave- head package measures only 125 × 70 great potential to overcome the limita-
length flexible and efficient mid-IR × 45 mm and is in-sensitive to varying tions in sensitivity and selectivity of the
well-accepted conventional FTIR spec-
troscopy. Experimental demonstrations
Companies of the OPO / CE-PAS capability were
performed with two different OPO’s
with wavelength ranges of 3237 – 3296
Cobolt AB, a part of HÜBNER Photonics nm (95 mW) and 3405 – 3463 nm
Stockholm, Sweden (110 mW). These OPO’s were coupled
Cobolt supplies high performance CW and Q-switched lasers, for stand-alone use into one of Gasera’s commercially avail-
or OEM integration in equipment for fluorescence analysis, Raman spectroscopy, able PA201 research photoacoustic de-
interferometric metrology, micromachining and environmental monitoring. The tector for laser sources.
Cobolt lasers are based on tailored nonlinear optical crystals for efficient frequen-
cy conversion and are manufactured in a compact and robust hermetically sealed
package using proprietary HTCureTM Technology, which provides outstandingly
high tolerance to demanding environmental conditions and ensured lifetime.

www.hubner-photonics.com
Gasera Ltd.
Turku, Finland

Gasera develops cutting edge measuring equipment that enables reliable analy-
sis of gases, liquids and solid materials. The technical know-how along with own-
ership of the intellectual property rights guarantee that all Gasera products meet
the high demands of today’s measuring equipment market.

www.gasera.fi Fig. 4 Cobolt Odin: Complete OPO system with all-integrated

laser head and driver unit.

© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Optik&Photonik 1/2017 37
 www.photonicsviews.com

ulated HITRAN spectrum and a detec-

tion limit was measured to be 3.3 ppb
(2×  rms, 1s channel integration time
CIT).
In the second demonstration [6],
the same OPO was used to measure
benzene, toluene and 3-xylene isomers
(namely, o-, p- and m-xylenes). The
samples were produced by evaporating
anhydrous liquid samples, with known
rate, into 1200 ml/min flow of nitrogen
(purity 6.0) and capturing a sample into
the photoacoustic cell from the sample
gas flow. The measured spectra were
analyzed with science based method,
as described in reference [6] resulting
Fig. 5  The OPO based CE-PAS measurement set-up. The Cobolt Odin is coupled into in multi-compound detection limits
Gasera’s PA201 photoacoustic detector. (3× rms) for benzene 4.3 ppb, toluene
7.4 ppb, p-xylene 11.0 ppb, o-xylene
0.35 0,00008 6.2 ppb and m-xylene 12.5 ppb.
CH4 (measurement, 10 ppm) 0,00007 In the third demonstration, a second
0.3

Absorption coefficient [cm-1]

CH4 (HITRAN, 1 ppm) OPO with tuning range from 3405 to
Photoacoustic signal [arb.]

0.25 0,00006
3463 nm, was setup to measure ethanol,
0,00005
0.2 methanol and methane with the PA201
0,00004
0.15 photoacoustic detector. The pulsed
0,00003 OPO used in this experiment (repe-
0.1
0,00002 tition rate 10 kHz, pulse width 4  ns,
0.05 0,00001 line width 1.1 nm and output power
0 0 112  mW) was electrically amplitude
3230 3240 3250 3260 3270 3280 3290 3300
modulated with 50 : 50 pulse ratio, i.e.
Wavelength [nm]
consecutively turning the 10 kHz pulse
Fig. 6  10 ppm of CH4 measured with OPO / CE- OPO / CE-PAS, with 3.3 ppb DL at 1 s inte- train on and off at a frequency of 70 Hz.
gration time. The sample gas components were nitro-
gen diluted from verified gas cylinders,
and the measurement pressure at the
0.18 photoacoustic cell was 1060 mbar. The
benzene 5.05 ppm
0.16
m-xylene 4.94 ppm respective univariate detection limits
0.14 obtained were (at 2× rms, with 1 s CIT):
o-xylene 4.96 ppm
Photoacoustic signal (a.u.)

for EtOH 7.7 ppb, for MeOH 11.4 ppb

0.12 p-xylene 7.20 ppm and for CH4 35 ppb. In this configura-
0.10 toluene 9.85 ppm tion, the total response time of the sys-
0.08 tem was about thirty seconds, includ-
0.06 ing the automatic gas exchange and the
signal processing for a reduced tuning
0.04
range.
0.02 With these demonstrations, we con-
0.00 clude that the compact design and high
3230 3240 3250 3260 3270 3280 3290 3300 mid-IR output power from the Cobolt
Wavelength [nm] Odin, combined with Gasera’s novel
cantilever enhanced photoaccoustic
Fig. 7  Measured spectra of benzene, toluene, o-, p- and m-xylene. measurement technology, allow the
OPO / CE-PAS technology to offer ex-
In the first measurement setup [5], a mechanical tuning fork chopper op- treme sensitivity and selectivity in re-
a collimated beam from the OPO was erating at a frequency of 135 Hz. The liable industrial gas analysis and mon-
directed through the photoacoustic sample gas contained 10 ppm of CH4 itoring. The demonstrated multi-gas
cell (path length of 95 mm) into an op- in nitrogen at 953 mbar in the photo- detection with ppb-level performance,
tical power meter. The pulsed emission acoustic cell. The sample gas spectrum is reachable with a wide variety of gas
from the OPO (repetition rate 10 kHz, was collected with steps of 0.1 nm with components in various applications.
pulse width 4 ns, pulse energy 5 μJ and integration time of 1 s per step. The re- And still, the full measurement system
line width 1.3 nm) was modulated with sulting spectrum was compared to sim- fits into a 19-inch, 3-unit rack mount,

38  Optik&Photonik 1/2017  © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Spectroscopy

[3] R. Lindley et al.: A sensitivity comparison of

1.6 0.01 three photoacoustic cells containing a sin-
gle microphone, a differential dual micro-
1.4
phone or a cantilever pressure sensor, Appl.
0.008 Phys. B 86 (2007) 707-713
1.2
Photoacoustic signal (a.u.)

[4] J. Peltola et al.: High sensitivity trace gas

Absorbance (ln-log, 95 mm)

detection by cantilever-enhanced photo-
1 0.006 EtOH 107 ppm
acoustic spectroscopy using a mid-infrared
Methanol 90 ppm continuous-wave optical parametric oscil-
0.8 Methane100 ppm lator. Optics Express 21 (2013) 8, 10240,
0.6 0.004 EtOH 107 ppm (PNNL) doi:10.1364/OE.21.010240
MeOH 90 ppm (PNNL) [5] Application note available from Web: www.
0.4 CH4 100 ppm (HITRAN) gasera.fi/uploads/application-notes/Ap-
0.002 pNote_CH4_OPO-PA201_29012013.pdf
0.2 [6] C. B. Hirschmann et al.: Trace gas detection
of benzene, toluene, p-, m- and o-xylene
0 0 with a compact measurement system using
3.4 3.41 3.42 3.43 3.44 3.45 3.46 cantilever enhanced photoacoustic spec-
Wavelength [µm] troscopy and optical parametric oscillator.
Vibrational Spectroscopy 68 (2013) 170–
176. doi:10.1016/j. vibspec.2013.07.004
Fig. 8  (6). 10 ppm of CH4 measured with OPO / CE- OPO / CE-PAS, with 3.3 ppb DL at 1 s
integration time.
Sauli Sinisalo
Gasera Ltd, Tykistökatu 4, 20520, Turku,
Finland,
with possibilities for further down-scal- [1] J. Li, W. Chen and B. Yu: Recent Progress
Ph. +358 40 522 26,
ing of the system, ultimately into hand- on Infrared Photoacoustic Spectroscopy
www.gasera.fi, sauli.sinisalo@gasera.fi
Techniques, Applied Spectroscopy Reviews
held size.
46 (2011) 6, 440–471 Håkan Karlsson
DOI: 10.1002/opph.201700002 [2] V. Koskinen et al.: Progress in cantilever CEO, Cobolt AB, Vretenvägen 13,
enhanced photoacoustic spectroscopy, Vi- 17154 Solna, Sweden,
brational Spectroscopy 48 (2008) 1, 1–6, Ph. +46 8 54591230, www.cobolt.se,
doi:10.1016/j.vibspec.2008.01.013 hakan.karlsson@cobolt.se

© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Optik&Photonik 1/2017 39