Optik 149 (2017) 288–294

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Optik
journal homepage: www.elsevier.de/ijleo

Original research article

Fabrication and characterization of down-tapered optical

fiber pH sensor using sol-gel method
Akhilesh Kumar Pathak ∗ , Vinod Kumar Singh ∗
Optical Fiber Laboratory, Department of Applied Physics, Indian Institute of Technology (Indian School of Mines), Dhanbad, Jharkhand,
India

a r t i c l e i n f o a b s t r a c t

Article history: In the present paper the fabrication and characterization of down-tapered optical fiber
Received 15 May 2017 based pH sensor have been reported. The sensing probe is formed by fusing single mode
Accepted 14 September 2017 fibers (SMF) to make it down-tapered which is spliced with multi-mode fiber (MMF). The
sensing region is immobilized with sol-gel prepared by mixture of tetraethyl orthosili-
Keywords: cate with three different pH indicators on to cladding of middle SMF. The proposed sensor
Down-tapered utilizes intensity interrogation method and operates in low and high pH values. The max-
pH sensor
imum sensitivity of 0.49 dBm/pH is obtained with a good linear response for wide range
Single-mode fiber
of pH value varied from 4 to 13. In addition to high sensitivity, this sensor has additional
Stability
Response time advantages of good stability, fast response time and capable of using in remote sensing.
© 2017 Elsevier GmbH. All rights reserved.

1. Introduction

The pH measurement is mostly required in many fields of sciences e.g. chemical, environmental and biomedical. Practi-
cally pH of acid and base solution is determined either by using paper strip or glass electrodes. Both types of sensors have
advantages and disadvantages e.g. paper strip can give only a rough idea instead of exact numerical value while glass elec-
trodes gives numerical value but they are expensive [1,2] and suffer poor performance with solution of low ionic strength.
These drawbacks of existing pH sensors motivate researchers to look forward for the development of other alternatives of
pH sensors. Amongst various kinds of available sensor technologies, optical fiber based sensors attract to scientific commu-
nity due to its fascinating features. The optical fiber based sensors possess cost effective fabrication, compact in size, highly
sensitive and no electromagnetic interference due to the presence of optical signal which makes fiber to use worthy in every
medium.
Several types of optical fiber sensors have been already fabricated and demonstrated with various sensing utilities [3–5].
The first optical fiber pH sensor was developed by Goldstein et al. in 1980 for physiological use, which works in the range
varied from 7 to 7.4 [6]. The phenol red was used as a sensing indicator and the sensor was based on the concept of color
detection when come in contact of various pH solutions. After year 1980, a revolutionary modification takes place in the field
of fiber based pH sensing. In this class of sensors the pH indicators are infiltrated in porous polymer via simply deposited
over the sensing area of fiber [7–9]. The change in spectral characteristics takes place when the pH solution comes in contact
with these coated indicators. By measuring these spectral changes we can get the corresponding pH value. In recent years,
the pH sensor is fabricated and further modified by changing their structures and the deposited sensing materials [10–13].

∗ Corresponding authors.
E-mail addresses: akhileshpathak57@yahoo.com (A.K. Pathak), vksingh@iitism.ac.in (V.K. Singh).

http://dx.doi.org/10.1016/j.ijleo.2017.09.051
0030-4026/© 2017 Elsevier GmbH. All rights reserved.
 A.K. Pathak, V.K. Singh / Optik 149 (2017) 288–294 289

Fig. 1. (a) Schematic image of formation of tapered portion in SMF and (b) SEM micrograph of tapered end of fabricated probe.

Table 1
Shows the chemical list with their used volume.

Solutions Quantity

TEOS 20 ml
Anhydrous ethanol 20 ml
Deionized water 1 ml
Cresol red 26 mg
Chlorophenol red 26 mg
Bromothymol blue 36 mg

Here, a cost effective pH sensor based on excitation of cladding modes in SMF is presented. The probe has been prepared
by immobilizing the indicators on the cladding after activating OH− group on it. In sol-gel preparation the mixture of three
pH indicators are used to obtain the wide pH range [14,15]. The leakage of launched light from the tapered portion causes
the excitation of cladding modes of SMF which interact with the analyte via deposited sol-gel. The changes in the power with
respect to the changes in pH are recorded by power meter. Investigations have been also carried out at different stirring time
to study the variation in sensitivity with viscosity of sol-gel. In previously reported papers the sensors are required large
probe size, chemical tapering and surface modification for better sensitivity [10,12,16] while our fabricated sensor requires
simple splicing and sol-gel deposition to achieve high sensitivity.

2. Probe fabrication

In fabricated probe, SMF and MMF of core/cladding diameter of 8/125 and 50/125 respectively were purchased from Thor
lab. The sensing probe was fabricated by fusion splicing method under optimized conditions as our previously published
article [17]. The plastic jacket was removed from 30 mm length of SMF and sensing matrix was deposited onto removed
jacket portion. The tapering process was done by using fusion splicer SUMITOMO T-39. Our sensor consists of a down-tapered
SMF at one end and stubbing of MMF at another end. Firstly, as shown in Fig. 1(a), two cleaned SMF was placed in the splicer
under optimized arc discharge to form ellipsoid heads and then fused together by giving further arc discharges to fabricate
down-tapered sensing head. Fig. 1(b) shows the microscopic image of the down-tapered portion fabricated in SMF.

3. Synthesis of sensing matrix and experimental setup

All materials used in the synthesis of sol-gel are purchased from Sigma-Aldrich. Sol-gel method is widely used in the
formation of chemosensors that requires low temperature to be produced. This method contains a complex reaction that
involves mixture of various solvent along with some metal alkoxide at low temperature to prepare a homogenous solution
[18,19]. The chemical which is used in the sol-gel preparation are listed below in Table 1 as per there used volume.
The sol-gel was prepared by mixing of 20 ml TEOS, followed by 20 ml of anhydrous ethanol, 1 ml of deionized water
along with 26 mg of cresol red and chlorophenol red respectively, with 36 mg of bromothymol blue. The mixture was then
stirred at constant temperature 60 ◦ C before being used. TEOS was used as a precursor which gives the porous silica glass
of less refractive index in comparison to the cladding to maintain the waveguide condition. Here we use three different pH
indicators due to their different pH ranges and hence their simultaneous mixing enhances the range and covered a broad
pH value [14,20,21]. Before deposition of sol-gel, the OH group was activated over the cladding region of SMF by treating it
with 69% HNO3 for 5 min.
To deposit prepared sol-gel on the cladded portion, dip coating method was used here out of various coating methods.
The speed of dip coater was fixed at 70 mm/min with the two minutes of wet and four minutes of dry time. When the cladded
portion is immersed and pulled in the prepared matrix, the activated OH group form bonds with the silica molecule and
290 A.K. Pathak, V.K. Singh / Optik 149 (2017) 288–294

Fig. 2. (a) Microscope image of bare fiber and fiber with deposited matrix prepared at 3 h stirring and 5 h stirring time (b) Schematic diagram of fabricated
sensing head.

help it to get adhered at the surface. Fig. 2(a) shows the microscopic image of deposited sensing film over cladded SMF for
different times, while 2(b) is the schematic diagram of sensing head.
During the stirring both hydrolysis and polycondensation reactions take place simultaneously. Here we have used two
stirring times (3 h and 5 h) in our study. The purpose of increasing stirring time is to get a viscose sol-gel by avoiding local
overheating and achieving full chemical reactions. The prepared sol-gel was placed for half an hour at room temperature in
order to cool the solution. The hydrolysis reaction takes place as mentioned below

Here, R represents C2 H5 .
The dealcoholization polycondensation reaction is performed as:

After the successful coating the fabricated probe is dried for 15 days at the room temperature and atmospheric pressure.
The 3-D structure of sol-gel matrix is formed during above hydrolysis and polycondensation reactions. The basic pH sensing
principle is based on the change in absorption ability of light. When the sensing head is immersed in pH solution, the
hydrogen ions of pH solution penetrate into the coated SMF probe due to the presence of mesh-gap. During this penetration
process these hydrogen ions react with the molecule of indicators which directly affect the absorption ability of input light.
Therefore, the density of hydrogen ions in pH solution leads to the variation of optical output power.
The experimental setup used in the study is shown in Fig. 3, which contains a laser source of wavelength 1550 nm, a power
meter and the fabricated sensing probe. The sol-gel deposited probe is placed in the cell carries the solution of various pH
values.
The light coming out from the source passes to the MMF through tapered portion. In this fabricated sensing probe the
tapered SMF works as a beam splitter used to excite cladding modes of SMF whereas MMF works as a beam coupler. The
basic significance of tapering and MMF is to split and recouple light in SMF. The excited cladding modes propagate through
the cladding region of SMF which directly interact with the outside solution of varying pH. These guided cladding modes
 A.K. Pathak, V.K. Singh / Optik 149 (2017) 288–294 291

Fig. 3. Experimental Setup used for the characterization of pH sensor.

recombine with the core mode in MMF which is connected with the power meter to measure the transmitted power. The
transmission in fabricated structure can be calculated with wellknown Fresnel coefficients [22].

4. Results and discussion

In the experiment the various concentrations of NaOH and CH3 COOH are used to change the pH of deionized (DI) water
and measured by digital pH meter. Since NaOH contains Na+ and OH− ions which float apart after dissolving in water and
lead to extra OH− in water. The increase in concentration of OH− makes the solution more basic and therefore dramatically
increases pH value.

An acetic acid (CH3 COOH) is used to decrease the pH of DI water. As Acetic acid contains CH3 COO− and H+ ions, it increases
the value of H+ ion in solution after dissolving in water, and hence pH value decreases. The basic reaction takes place after
dissolving CH3 COOH in DI water which can be written as follows

CH3 COOH → CH3 COO− + H+

In the fabricated sensing probe, light from the laser source is launched in the coated fiber placed on the dish filled with
the pH solution in which the middle coated portion of the fiber is immersed. The launched light gets leaked from the tapered
portion consequence of which the excitation of cladding modes take place, and these excited modes again recouple in SMF
through MMF. The output power is recorded for several studies e.g. pH sensing, repeatability, stability and time responses.
The experiment is performed on two types of solution prepared at different stirring times of 3 h and 5 h. Firstly, the output
responses is measured for the sensing structure immobilized with sol-gel stirred at different stirring time under constant
temperature 60 ◦ C. Fig. 4 shows the variation of power with a broad range of pH value varied from 4 to 13. The regression
equations of the obtained experimental data at 1550 nm laser source, may be written as follow

P (dBm) = (−19.32) + (−0.24) × pH (1)

P (dBm) = (−19.78) + (−0.49) × pH (2)

Where, P shows the output power. Eqs. (1) and (2) give the regression equations for experimental data recorded at 3 h and
5 h of stirring. The sensitivities obtained from linear fitting of graph are 0.24dBm/pH and 0.49dBm/pH at 3 h and 5 h stirring
time respectively. The increase stirring time gives a good linear response of P-pH curve which is about 0.98 to our fabricated
sensor. Here the improvement in sensitivity may arise due to increase in the viscosity of 3-D sol-gel. As observed from Fig. 4,
the output power decreases with increase in pH around the sensing probe due to the variation in density of hydrogen ions in
pH solutions [15]. The variation in power and hence sensitivity completely depend upon the density of hydrogen ion in pH
solution and the viscosity of prepared sol-gel. 3 h stirred sol-gel is difficult to stick with fiber due to its less viscous property
while it becomes more viscous after 5 h stirring time and hence can be easily and uniformly deposited over sensing region.
292 A.K. Pathak, V.K. Singh / Optik 149 (2017) 288–294

Fig. 4. Power response plot of fabricated pH sensor 3 h and 5 h of stirring time.

Fig. 5. Repeatability response recorded over 10 days.

The uniform coating of sensing matrix can interact with evanescent waves and gives good sensitivity to the broad range of
pH value.
After investigation of sensitivity, the same probe with 5 h stirred matrix is used to study the repeatability response. The
observed output response as recorded at different durations is shown in Fig. 5. Initially, after performing first day experiment,
the probe has been washed properly by using buffer of 7 pH value and left in dark before it can be used on the fifth day.
The same process of examination is carried out on fifth day and tenth day. The sensitivity of 0.49 dBm/pH, 0.46 dBm/pH
and 0.44 dBm/pH is obtained for 1st day, 5th day and 10th day respectively. As we can see from Fig. 5, there is very slight
decrease in sensitivity as observed over 10 days of examination.
The correlation between output power and the response time is shown in Fig. 6. There are various factors that affect the
response time like thickness of sol-gel, particle size, concentration of indicator solution and the shape of sensing structure.
The thick coated probe with large particle size causes the difficulty in interaction of sensing material with the pH solution.
To record the response time the probe is first placed in air and the output power is measured. It is then immersed in the
solution of a lower pH = 5 and again the output power is noted. When the output power approaches to a constant value, the
probe is suddenly placed in the solution of higher pH = 11 and again the output power is measured. The process is repeated
for several times through which we obtained the good response time of nearly 6 s.
The stability of indicators is the most important factor on the basis of which they are selected in pH sensing. To investigate
the photostability the same experimental setup was used as shown in Fig. 3. The experiments were performed for both the
acid and base, for which the probe is initially immersed in solution of pH value 5 and later in a solution of pH value 11. Here
Fig. 7 depicts the power response for both solutions examined over 70 min at the difference of 10 min. For pH = 5 the power
varies between −22.13 dBm to −22.15 dBm while for pH = 11 it varies from −25.29 dBm to −25.32 dBm which is almost
stable. Hence we can say that no such surface degradation is observed during such a long time period of 70 min. Thus our
indicators have superior photostability and can be used for continues monitoring.
 A.K. Pathak, V.K. Singh / Optik 149 (2017) 288–294 293

Fig. 6. The response time curve for prepared sensing head.

Fig. 7. Schematic plot for stability response recorded over 70 min.

5. Conclusion

In this paper a wide range of pH sensor is demonstrated by immobilizing the mixture of various pH indicators. A
large number of experiments are performed to investigate the sensitivity, repeatability and response time. A high sen-
sitivity of 0.49 dBm/pH has been achieved by fabricated sensing head with excellent stability, good durability and fast
response time. Furthermore, the low cost fabrication, compact size and its robustness make it useful for the study of pH in
microenvironments.

Acknowledgements

The whole experimental work is demonstrated in our Optical Fiber Laboratory, Department of Applied Physics, IIT(ISM).
Authors are thankful to IIT(ISM), Dhanbad for providing funding support for experiment. Authors are also thankful to Dr. M.
R. Singh, Department of Applied Physics, IIT(ISM) for providing lab facility for microscope imaging of our fabricated sensing
probe.

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