Sensors and Actuators B 106 (2005) 518–522

Design and characterization of pH sensor based on

sol–gel silica layer on plastic optical fiber
E. Alvarado-Méndeza,∗ , R. Rojas-Lagunaa , J.A. Andrade-Lucioa , D. Hernández-Cruzb ,
R.A. Lessardb , J.G. Aviña-Cervantesc,1
aDepto. de Electrónica, Facultad de Ingenierı́a Mecánica, Eléctrica y Electrónica, Universidad de Guanajuato,
Apartado Postal 215-A, Salamanca, Gto. 36730, México
b COPL, Department of Physics, Engineering Physics and Optics, Laval University, Québec, Que., Canada G1K7P4
c LAAS/CNRS Laboratoire d’Analyse et d’Architecture des Systèmes, 7 Avenue du Colonel Roche, 31077 Toulouse, France

Received 26 February 2004; received in revised form 27 July 2004; accepted 28 July 2004
Available online 5 November 2004

In memory of our friend Gustavo E. Torres-Cisneros.

Abstract
In this paper, design and characterization of a pH optical fiber sensor with pH sensitive dye is described. The sensor is prepared by fixing
the doped plastic fiber on a fused ortosilica block surface with blue bromophenol. The surface charge of silica and the refractive index, which
plays an important roll on the fiber, modifies the conditions of light propagation into the plastic optical fiber. We use the transmittance to
measure the pH of a solution or fluid in a range between 5.0 and 7.0. The advantage of this sensor is that, only 2 cm of doped fiber is enough
to measure the pH of a fluid in real time. The time response of the sensor reported in the present study is approximately 10 s.
© 2004 Elsevier B.V. All rights reserved.
PACS: 42.65Wi; 42.65Tg; 42.65H

Keywords: Optical fiber; Sensor; Absorption; pH; Sol–gel

1. Introduction small size, explosion proof, remote sensing, possibility of

The interest in measuring and controlling the pH of flu-
ids, or organisms in chemistry, biomedics, cosmetics, food,
and environmental areas is very important from a practical
point of view [1–3]. Considering pH sensor technology, it
is a challenge to obtain cheaper and more accurate sensors.
In recent years, numerous efforts have been directed towards
the development of optical fiber pH sensors [4–6]. Optical
fiber pH sensors are based on pH-induced reversible changes
in optical or spectroscopic properties such as the absorbance,
reflectance, transmittance, fluorescence, energy transfer, etc.
Their principal advantage over other types of sensors, as the
electronics, is the immunity to electromagnetic interference,
∗ gel technology has several advantages over other methods of
Corresponding author. Tel.: +52 464 6480911; fax: +52 464 6472400.
E-mail address: ealvarad@salamanca.ugto.mx (E. Alvarado-Méndez).
1 CONACyT.
multiplexing, etc. The main component in an optical fiber
sensor is a pH sensitive dye deposited onto the tips or ex-
tremes of an optical fiber. To immobilize the dye, many re-
search groups have used –gel technology [7–13]. In this tech-
nique, a thin film of glass with entrapped dye is prepared from
the hydrolysis, condensation and polymerization of a metal
alkoxide solution followed by a densification process. The
sol–gel method is one of the most readily exploited tech-
niques of transducer immobilization. It enables creating a
glass-like porous structure at room temperature, by entrap-
ping the element transducer (usually organic compounds) in
a rigid network of silica. Moreover, easy tailoring of the silica
matrix properties is possible by changing the sol composition
and gelation conditions and the gel treatment [14]. The sol–
film deposition. The film produced is inert and more resistant
than polymer films in aggressive environments. The probe is

0167-0987/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2004.07.020
 E. Alvarado-Méndez et al. / Sensors and Actuators B 106 (2005) 518–522 519

prepared by immobilizing a pH-sensitive dye on the surface

of the fiber. Moreover, data acquisition in real time is very
important for the sensor performance.
Some biological systems have ionic groups which elec-
trical charge depends on pH concentration; this pH value
depends on the balance between the O–H and H. Therefore,
pH is sensitive to the ions concentration in a solution. The
electric charge in each organism depends on this value. Un-
der certain pH conditions or situations, an organism can be
neutralized or it can drastically change its charge, in conse-
quence, its functions change too. That is the importance of
pH measure value in real time [15].
In this work, we developed a sensor in which the acqui-
sition and processing of an optical signal(transmitted by an
optical fiber) is realized in real time by means of a computer.
The whole system is controlled by a LabView® program. The
sensor can take lectures each 0.5 s (it means at 1, 1.5, 2 s, etc.),
in consequence it is possible to obtain the characteristic curve
of the sensor performance while it is measuring the pH value.
The results of the pH optical plastic fiber sensor based on
light transmittance of the a sol–gel film deposited on its tip, Fig. 1. FTIR of the fiber optic within doped (continuos line) and doped
(dashed line).
are reported. The intrinsic properties of the plastic optical
fiber were used to determine the pH in a range between 5.0
gerprints at 3358 cm−1 , can be related to the silica formation
and 7.0.
arising from tetra-ethyl-orto-silicate (TEOS) on the fiber. The
shift or deformation around the 1006 cm−1 , could represent
the Si–O–Si bonds, it means, the reaction between the silica
2. Film preparation
on fiber surface and the silica arising from TEOS. Other im-
portant characteristic is around the 1590 cm−1 , it means, the
The plastic optical fiber has a diameter core of 750 ␮m
and a numerical aperture (NA) of 0.20. The sol–gel depo-
sition process on the fiber, starts by removing the cladding,
approximately 0.5 cm, on each extreme of the fiber by means
of a surgical blade and then cleaning it with acetone. After
cleaning, the OH groups on the fiber core were activated by
cleaning it to a 30% HNO3 solution. Then, to prepare the so-
lution, we use tetraethyl ortho silicate (TEOS) and we follow
the method described in [12], by mixing 1 ml of TEOS, 1 ml
of ethanol, and 0.1 ml of de ionized distilled water along with
1.49 mg of bromo phenol blue at room temperature. Then it Fig. 2. Scheme of the optical measurement set up.
was stirred for 30 min at 60 ◦ C, before being ready to be used.
When we submerged and pulled out plastic fiber from the
prepared sol, the activated OH groups on the surface of the
fiber core form bonds with the silica molecules in the porous
glass film and help it to be adhered to the surface. This thin
film deposition process, was modified by immersing the fiber
for 15 days at atmospheric pressure and room temperature.
Then, the fiber was thermally treated for 1 h at 90 ◦ C. We ob-
serve that this long deposition process and high temperatures
treatment improves the adhesion of the dyes to the plastic
optical fiber, obtaining the final doped fiber (optrode).
Infrared spectroscopy, was used to identify the presence
of certain functional groups in a molecule. Also, one can use
the unique collection of absorption bonds to identify specific
impurities. The FTIR spectra obtained for a single plastic
fiber (dashed line), and a plastic doped fiber (solid line) are
showed in Fig. 1. In this figure, we can find that the fin- Fig. 3. Characteristic curve of the sensor in mV vs. pH for different buffers.
520 E. Alvarado-Méndez et al. / Sensors and Actuators B 106 (2005) 518–522

blue bromophenol modify the initial spectrum of the optical
fiber.
3. Experimental setup
The experimental setup to characterize the pH sensor is
shown in Fig. 2. Light from a LED (632.8 nm.) was injected
into the doped fiber, while the other extreme was immersed
in a buffer fluid of known pH. To obtain the characteristic
curve, we use some known buffers (pH from 5 to 7). The
outgoing signal from the photodetector, related to the pH
value, is traced and showed in Fig. 3. A linear behavior was
observed, this is confirmed by the results obtained by Gupta
et al. [9].
As we mentioned, the intensity variation, due to the differ-
ent buffers values, is converted in a voltage variation by the
photodetector. This signal, is acquired and processed using
LabView® . The system operation is showed in the diagram of
Fig. 4. The input signal is composed by two measurements:

Fig. 4. Scheme of LabView program functionality.

Fig. 5. Interpolation curve on the frontal panel in real time.

 E. Alvarado-Méndez et al. / Sensors and Actuators B 106 (2005) 518–522
Fig. 6. Fiber optic absorbance with a sol–gel matrix for different wave-
lengths.
the first one corresponds to the measured value without buffer
and the second one to the value with buffer. We make the
subtraction of those voltages and the resulted valued is in-
terpolated with those from characteristic curve (20 samples
each 50 ms), obtaining the real pH value.
Finally, this value is displayed in real time on a interpo-
lation curve on the frontal panel (Fig. 5). This panel permit
us to follow the pH behavior, on the displayed graphic, along
the measurements and to make the registration of those values
(with date and time), on a text file generated by the LabView®
program (VIs).
The optimal wavelength operation for this sensor was de-
termined using a spectrophotometer (Cary 500), ranging from
300 to 1600 nm. The maximum fraction change in power (ab-
sorbance), of the doped optical fiber was around 480 nm (see
Fig. 6). Nevertheless, around 632 nm (used wavelength), we
have the 75% of absorbance. It could be a disadvantage, but
it can be tolerated because of the short length of the light
propagation into the plastic fiber ( 2 cm from the LED to the
photodetector). Is for that reason that we decide to use the
LED at 632 nm, which is easier to find in the market.
4. Results and discussion
Our system is practical and easy to use, we just need to dip
the tip of the fiber into a pH buffer and then introduce it into
our system to make the acquisition and data processing. The
voltage variation as a function of the measured pH, was found
to be linear in the pH range from 5 to 7. This measurement,
was carried out varying (increasing and decreasing) the pH
value and was repeated several times. The reproducibility of
the measurements was obtained in almost all the attempts.
The lost of transmitted power was around 40% for a pH of
7.0.
In summary, the plastic optical fiber pH sensor based on
sol–gel technique with blue bromophenol, have advantages
521
over other similar sensors. The acquisition card stability and
resolution, permit us to make the data process in real time.
The plastic optical fiber was characterized and its behavior
was studied, its response time was about 10 s. Studies using
remote sensing and data transfer are being developed and will
permit us to use is as a portable system, the results will be
showed in further communications.
Acknowledgements
This work was supported by CONACyT, projects: J32018-
A, J35313-A, and J3881-A, CONCYTEG-5987-FONINV,
“Apoyo a la maestrı́ a en Ing. Eléctrica”. The author thanks
the support of the CONACyT. This work has been partially
funded by the French-Mexicain Laboratory on Computer Sci-
ence d’Informatique.
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Biographies
Edgar Alvarado-Méndez received his PhD degree with honours in op-
tics from the National Institute for Astrophysics, Optics, and Electronics in
Puebla, México in 1997. He is currently research and teacher in the Fac-
ulty of Engineering Mechanics, Electrical and Electronics (FIMEE) in the
University of Guanajuato, México. His main activities are in experimental
optical sensors based in fiber optics and theoretical nonlinear optics.
Roberto Rojas-laguna received his PhD degree in optics from the National
Institute for Astrophysics, Optics, and Electronics in Puebla, México in 1999.
He is currently research and teacher in the Faculty of Engineering Mechanics,
Electrical and Electronics (FIMEE) in the University of Guanajuato, México.
His main research activities are in nonlinear effects in fiber optics, Raman,
and sensors with fiber optics.
José A. Andrade-Lucio received his PhD degree in optics from the National
Institute for Astrophysics, Optics, and Electronics in Puebla, México in 1999.
He is currently research and teacher in the Faculty of Engineering Mechanics,
Electrical and Electronics (FIMEE) in the University of Guanajuato, México.
His main activities are in experimental nonlinear optics, optical sensors and
optical signal processing.
Daniel Hernández-Cruz was born in Tuxtla Gutiérrez, Chiapas, México,
and received the BS degree in electronics engineering from the Technical
Institute at Tuxtla Gutiérrez (ITTG), in Tuxtla Gutierrez, Chiapas, México
in 1997. He earned his MSc degree in optics from the National Institute for
Astrophysics, Optics, and Electronics, in Puebla, México in 1999. He is
currently studying his PhD at Laval University in Quebec, Canada, in the
optical materials group, at the department of Physics, Engineering Physics
and Optics. His research interest includes the fabrication and characterisa-
tion of optical materials, waveguides, photorefractives, optoelectronics and
optical communications.
Roger A. Lessard (PEng, PPhys, CQ) is a full professor (1982) and chair-
man (2000) of the Department of Physics, Engineering Physics and Optics of
the Faculty of Sciences and Engineering, Laval University, Quebec; Faculty
member of Physics since 1972. Founder director of the Center for Optics,
Photonics and Lasers (COPL) of the Faculty of Sciences and Engineer-
ing, Laval University in 1989, director from 1989 to 1994. Cofounder and
president of Laser InSpeck Inc. (1993–1996) (now InsSpeck); cofounder
of Holospectra (Lasiris) in 1985, research scientist at Gentec (1971–1972).
President of Roger A. Lessard D.Sc. Inc.; he is invited professor in the De-
partment of Precision Instrumentation of Tianjin University since 1982. Cur-
rent research interests are holography, holographic materials, holographic
and optical storage photonic materials and instrumentation. He gave more
that 100 conferences, more than 110 communications with proceedings, 190
communications in international and national conferences and is author of
122 publications and chapter of books. He supervised 18 PhD thesis, 25 MSc
thesis and he is currently supervising 15 graduate students at PhD (9) and
MSc (6).
J. Gabriel Aviña-Cervantes He is currently a PhD student in signal and
image processing at the National Polytechnics Institute of Toulouse, France.
His main research interest involves optoelectronics instrumentation, pattern
recognition, methods for the description and interpretation of outdoor natural
scenes and autonomous vision-based mobile robotics.