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A review on pH sensitive materials for sensors and detection methods

Article in Microsystem Technologies · October 2017

DOI: 10.1007/s00542-017-3495-5

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Microsyst Technol
DOI 10.1007/s00542-017-3495-5

REVIEW ARTICLE

A review on pH sensitive materials for sensors and detection

methods
Muhammad Imran Khan1,2 • Koushik Mukherjee3 • Rizwan Shoukat4 •

Huang Dong2,5

Received: 10 June 2017 / Accepted: 12 July 2017

 Springer-Verlag GmbH Germany 2017

Abstract This article focuses on the review of current
material and techniques for the selection of best combi-
nation among the pH sensitive materials related to pH
detection methods and sensors. Researchers have studied
various pH sensitive polymers, chemicals and found that
few measurement techniques do not have enough accuracy
to observe the pH when salt is present and this has been
examined further. The current work is based on compre-
hensive literature survey and discusses a variety of pH
sensitive materials for detection methods using different
sensors including their applications, mechanism of action
and merits, demerits. This analysis leads to a conclusion
that there are a number of important properties of the pH
sensitive material and the matrix, which has to be consid-
ered in the light of a target application finally dictating the
characteristics of the sensor. In many cases, a combinato-
rial approach of two pH sensitive materials or sensors
seems to be more effective with better real time response,
sensitivity, sensor resolution and operational stability in
place of the common standard techniques.
1 Introduction
During the last few years, micro and nano system based
technology has been changed and improved to a great
extent. MEMS based pH sensors have applications in many
areas including medical, military, aerospace, automobiles,
games, video and photo cameras etc. This article explores
the various pH sensitive materials and detection methods.
The main applications of pH measurements are present in
chemical and bio labs due to their dependency on pH.

1.1 Why pH is important

Muhammad Imran Khan and Koushik Mukherjee are equally
contributing authors. All processes whether chemical/biological/biochemical
processes are reliant on pH. The pH measurement is
& Muhammad Imran Khan required in determining the chemical characteristics and
imran@alumni.chalmers.se
behavior of a material. Both the solubility of biomolecules
1
Department of Electronics Engineering, University of or chemicals and chemical reaction kinetics are pH
Engineering and Technology (UET), Taxila 47050, Pakistan dependent. To control and prevent unwanted chemical
2
Micro-/Nano Electronic System Integration R&D Center reaction and optimize desired beneficial reactions, the
(MESIC), University of Science and Technology of China control of pH is essential.
(USTC), 230027 Hefei, Anhui, China
3
• The plants and animals living inside lakes, oceans and
STEERlife, Bangalore 560058, India
rivers determine their pH value. The presence of
4
Department of Microsystems Engineering-IMTEK, wastewater and waste products discharged from chem-
University of Freiburg, 79110 Freiburg, Germany
ical industries or factories impact water pH value and
5
School of Electronics Engineering, Xi’an University of Posts the existence of hazardous chemicals and materials
and Telecommunications, 710121 Xi’an, China

123

present can be observed inside the clean water. Hence
pH is an important indicator of environmental moni-
toring (water quality).
• pH has significant importance since enzyme catalyzed
chemical reactions of life are pH dependent. Significant
biochemical reactions like deactivation/denaturation of
proteins depend on pH resulting in non-functional and
dead cells.
• Soil pH is a crucial factor in agriculture. Crops have
healthy growth in most cases where pH is close to
neutral (pH 6–7.5) since the absorption of nutrients
from soil is impacted by pH.
• Lots of the industrial processes including semiconduc-
tors, food, drugs, cement and textile, pharma, consumer
goods, etc. are dependent on the pH measurements. pH
is also important in biomedical applications, biopro-
cesses and food spoilage monitoring.
1.2 What is pH?
Hydrogen ion is a very common species encountered in
most chemical reactions. pH stands for power of hydrogen
and is used to explain the acidic and basic nature of solu-
tion (Yuqing et al. 2005). For an aqueous solution, we can
write
H2 O $ Hþ þ OH
Equilibrium occurs in water between alkali (OH-) and
acid H?. pH determines the basicity or acidity of the
substance. Mathematically, we can write the pH value as
pH ¼ loga Hþ
where a = degree of dissociation.
The acidity or basicity of a solution is mentioned by
using pH value at a given temperature. Usually the pH
range is between 1 and 14. The solution will be acidic for
pH value range between 1 and 6, for the pH value of 7 the
solution will be neutral and solution in the range of 9–14 is
basic.
123
Microsyst Technol
Examples of solutions on the pH scale compared to
distilled water are set out below:
• pH = 0 =[ Battery acid which is very strong
Hydrofluoric acid
• pH = 1 =[ Hydrochloric acid secreted by stomach
lining
• pH = 2 =[ Lemon Juice, Gastric Acid, Vinegar
• pH = 3 =[ Grapefruit Juice, Orange Juice, Soda
• pH = 4 =[ Tomato Juice, Acid Rain
• pH = 5 =[ Soft Drinking Water, Black Coffee
• pH = 6 =[ Urine, Saliva
• pH = 7 =[ ’’Pure’’ Water
• pH = 8 =[ Sea Water
• pH = 9 =[ Baking Soda
• pH = 10 =[ Great Salt Lake, Milk of Magnesia
• pH = 11 =[ Ammonia Solution
• pH = 12 =[ Soapy Water
• pH = 13 =[ Bleach, Oven Cleaner
• pH = 14 =[ Liquid Drain Cleaner such as ‘‘Draino’’.
2 Detection techniques
This paper explores different pH detection methods and
materials including: Litmus paper, pH paper, ISFET based pH
sensor, pH image sensor, optical fiber pH sensor, fluorometric
pH sensor, ratiometric pH sensor, CCD camera full range pH
sensor array, wireless pH sensor, magnetoelastic pH sensor,
conductimetric pH sensor, cantilever pH sensor, glass electrode
and potentiometric pH sensors. The pH sensors can be broadly
classified under conventional, optical and electrical sensors.
2.1 Conventional methods
2.1.1 Litmus paper (indicators)
In early days, pH was measured using chemical indicators
like litmus paper that changes color with variation in pH.
Mixture of water-soluble dyes extracted from lichens like
Roccella tinctoria are absorbed into filter paper stripes to
make litmus paper. In this mixture, there are about 10–15
types of dyes. There are two types of litmus papers as blue
and red. For example, when dipped in basic solution
(pH [ 8) the litmus turns blue while in solution (pH \ 6)
that is acidic, it changes the color to red. It remains purplish
in a solution with a pH between 6.0 and 8.0. Since, most
processes chemical in nature are pH dependent, almost all
aqua samples need to have their pH tested at certain point.
Pros & Cons It’s a quick method to distinguish between
acids, bases, and neutrals, as the color change is fast. The
equivalence point is between pH 6.0 and pH 8.0, so it’s
acid range is equal to its base range. It’s also cheap.
Microsyst Technol

The disadvantage is the color change does not indicate

how strong the acid or base is. It doesn’t work so well in
non-polar liquids.

2.1.2 pH paper

pH papers are also easy to use. They are common in every

chemical laboratory which come in several types as rolls,
stripes, etc. Although pH meter is the best equipment to
measure the pH value accurately, pH papers are the very
suitable alternative for quick and approximate measure-
ments. While litmus paper only indicates acidic or basic
nature of solution, pH paper can give range and more
precise readings. A color chart is provided with pH paper.
This color change is relevant to the pH of the solution.
Pros & Cons They give fast and accurate readings for
the most part, easy to use (does not need expert knowl-
edge), portable, inexpensive. Sometimes the colors are not
contrasting, enough to determine the pH range which
prevents determining the value. Also, pH papers provide a
pH range, so the exact value cannot be determined.

2.1.3 Glass electrode pH sensor

It is possible to perform the pH measurement of an aqueous

solution by comparing the potential of known H ions
solution to the unknown H ions solution. It is hard to
determine the pH of solution directly. Two cells are used to
measure the potential between the two solution, one is
referred to as reference half-cell and other is sensing half-
cell.
Reference half-cell consists of an electrode as external
reference which is normally coated with Ag/AgCl
immersed reference electrolyte solution, and is also known
as salt solution. The other part of the reference electrode is
porous plug which allows the salt solution to go inside the
process solution but doesn’t allow process solution to get
inside the salt solution. This porous plug is basically
used to establish the electrical potential and is also known
as reference potential (Fig. 1).
Sensing half-cell consists of an internal half reference
electrode of Ag/Agcl, immerged in constant pH solution.
Instead of porous plug, glass membrane with hydrated gel
is used in sensing half-cell. Hydrated gel is coated on the
both sides of the glass membrane. When this chamber is
placed in the sample solution, metal ions, e.g. Na? ions on
the outer side of the glass membrane are replaced with H?
Fig. 1 Working principle to a pH Meter. Source: Nielsen SS (2010).
Food Analysis. 4th Edition. New York: Springer Science and
Business Media, LLC (http://www.azosensors.com/article.aspx?Arti
cleID=34)
ions in the solution. Due to this change in energy, electric
potential is changed. The change in the potential difference
between the two electrodes is measured by using voltage
measuring device like voltmeter (http://www.azosensors.
com/article.aspx?ArticleID=34).
Mathematically the potential difference is measured as:
E ¼ Einternalreference þ Emembrane þ Eporousplug
 Eexternalreference
By using the Nernst equation, the potential of the glass
electrode of half cell can be measured as
E ¼ E0 þRT
nF lnðaÞ
where E0 is the change in the internal and external refer-
ence potentials. R is universal gas constant and its value is
8.314 J/K.mol. F is Faraday’s constant. Its value is
F ¼ 9:6490  107 coulombs=kmol

123

‘‘n’’ is the number of negative charges transferred in the
solution. a is the activity of the ions and called reaction
quotient.
Pros & Cons While the glass electrode provides fast,
accurate and reliable reading it also suffers from drawbacks
like fragile materials, complex construction and frequent
calibration needs. For these reasons, they are also not ideal
candidates for miniaturization.
2.2 Electrode modification by pH sensitive polymers
Organic conducting polymer modified electrodes
(OCPMEs) have emerged as potential candidates for
electrochemical biosensors due to their easy preparation
methods along with unique properties, like stability in air
and being compatible with biological molecules in a neu-
tral aqueous solution. OCPMEs are playing an important
role in the improvement of public health and environment
for the detection of desired analyte with high sensitivity
and specificity. Electrodes modified with conducting
polymers like electropolymerized pyrrole, aniline, thio-
phene, or benzene derivatives are good substitutes for pH
electrodes (Herlem et al. 2001; Talaie 1997; Deronzier and
Moutet 1996; Komura et al. 2000; Davis et al. 1998;
Mahaveer et al. 2001). However, pH measurement using
this technique are unreliable due to defects and pinholes
present in the films structure. Herlem et al. (Herlem et al.
2001) reported a pH sensor, where a platinum electrode
was coated with thin linear PEI generated from anodic
oxidation of ethylene diamine. The mechanism by which
L-PEI responds to the change in pH is the protonation and
deprotonation of the numerous amino groups with varying
Fig. 2 Example of the working principle for optical fiber pH sensor.
Reprinted with permission from (Yuqing et al. 2005)
123
Microsyst Technol
pH present in its chemical structure other example of
electrodes modified with pH-sensitive polymers include
galvanostatic electro polymerization of monomers like,
pyrrole (Py), 3-(2,5-dihydroxybenzyl)pyrrole (PyQH),
aniline (An) and o-phenylenediamine (oPD) as reported in
(Santiago et al. 1999).
2.3 Optical method based sensors
2.3.1 Optical fiber pH sensors
The principle of optical fiber pH sensor is based on poly-
mers that can sense color change as shown in Fig. 2.
First example Few optical fiber pH sensors work on the
principle of adsorption of dyes like methylene blue dye on
the surface, which thereby generates absorption in the
evanescent field around fiber (Yuqing et al. 2005). pH
range of optical fiber pH sensors is between (3 – 9).
Second example Synthesized bases like (1) N,N0 -bis(4-
diaminobenzyliden)-1,2-cyclohexandiamine (2) N,N0 -
bis(4-diaminobenzyliden)-1,2-ethanediamine (3) 2,6-
bis[(4-dimethylaminopheylimino) ethyl]pyridine exhibits
optical response relative to absorption and emission
(Yuqing et al. 2005). They have pH range between 3 and
7.8. Bases 1 and 2 show weak emission while base 3 shows
strong emissions based responses (Yuqing et al. 2005).
Pros & Cons Optical fiber sensors have fast response,
non-contact measurements, no special storage conditions,
continuous measurement capability, low energy consump-
tion, low production cost, possibility of mass production
and measurement in biological pH range are additional
advantages. They also do not require reference sensor. The
sensors can resolve to 0.01 pH units with certain optical
configurations.
The disadvantages are limited long-term stability
because of photo bleaching and dye leaching along with
dependence on temperature.
2.3.2 Fluorometric pH sensor
Fluorescent pH indicators are an important bioanalytical
tool for measuring intercellular pH. A wide range of
organic dyes with pH-dependent optical properties is
available for pH monitoring by means of fluorescence
microscopy or other techniques relying on cell fluorescence
analysis. A large no of optically active molecular indicators
which are generally weak acids and have distinct spectral
and optical properties which vary on their protonated and
Microsyst Technol
Fig. 3 Absorption spectra recorded for Poly-aniline film in varying
pH buffer solutions. Reprinted from (Wang et al. 2010)  2007 with
permission from Elsevier
deprotonated state are used for intracellular pH sensing.
Some common examples are carboxyfluorescein-20 ,70 -bis-
(2-carboxyethyl)-5-(and-6)-carboxyfluorescein, 1,4-dihy-
droxyphthalonitrile, 8-hydroxypyrene-1,3,6-trisulfonic acid
(HPTS)1.
Seminaphthorhodafluor(SNARF)/seminathofluorescein
(SNAFL) dyes, boron-diupyrromethene (KBH-01) (Lakard
et al. 2004).
Pros & Cons They can be miniaturized to submicron
diameter, do not suffer from electromagnetic and electrical
interference.
One of the biggest disadvantages of fluorescent pH
sensor is that of measuring a signal which depends on the
ionic strength of the sample. This arises because of the
complex relation between the pH sensitive dye concentra-
tion and proton activity. However proper choice of dyes
with right chemical substituent in the dye can help nullify
this (Fig. 3).
Examples of commonly used optically active molecular
indicators for intracellular pH sensing are: polymers com-
plex in nature that have chromophore groups based on
change in pH are emerging for better pH sensing. A
number of polymers were explored for their fluorescent
property related to their pH sensitivity by Bojinov et al.
(Bojinov et al. 2008). Figure 4 shows the changes in the
fluorescence emission spectra of 1,2,2,6,6-pen-
tamethylpiperidin-4-ol as a function of pH.
Fig. 4 Fluorescence intensity (kex = 370 nm) vs. pH effect of
1,2,2,6,6-pentamethyl-piperidin-4-ol. Reprinted from (Bojinov et al.
2008)  2007 with permission from Elsevier
2.3.3 Ratiometric pH-dot sensors
Ratiometric pH sensor works on the principle where the
change in ratio of the emission or fluorescent peaks of two
chemical species is monitored with change in pH.
Example for ratiometric pH sensor is the application of
pH sensitive dyes Carboxynapthofluorescein (CNF) and
ETH 5350. The fluorescent peaks of the two dyes has two
peaks whereby the ratio of the peaks changes with pH.
Significant alteration in optical properties of ETH 530
coating were observed with pH change over pH 2.0 to pH
11.5 (Mcnaughton et al. 2005)
Pros & Cons The sensors are very useful in accurate
quantification of intracellular pH which has very signifi-
cation in understanding cellular activities and early warn-
ing of diseases. They help in circumventing the photo
bleaching of dyes, the auto fluorescence background aris-
ing from UV excitation. They are also minimally impacted
by drifts in the instrument or the fluctuation of the exci-
tation source, which often prevents accurate pH
determination.
The disadvantage is since two separated signal mea-
surements are required in ratiometric detection, change in
light sources and filter sets may result in time-shifted
recording & in worst case change the measurement
geometry. The leaching of the embedded dyes from the
matrices is also a matter of concern sometimes.
123

2.3.4 Holographic pH sensor
Measurement of pH using holographic pH sensor is a new
advancement. By incorporating ionizable monomer into
polymer based hydrogel films that are converted into vol-
ume hologram combined with holographic recording using
Nd:YaG laser (532 nm). Swelling behavior and shrinkage
due to change in pH are measured by the diffraction
wavelength of the holograms. Holographic sensors when
optimized can have milli-pH resolution sensitivity and are
reversible in nature with pH measurement over extended
period of 40 h. Using different polymeric species like
poly(hydroxyethylmethacrylate-co-methacrylic acid) and
hydrogel made from poly(2-hydroexyethylmethacrylate)
and 2-(dimethylaminoethyl methacrylate). Holographic pH
sensors can be used in different applications like 1) mea-
surement of blood plasma ex vivo and also real time.
Pros & Cons Holographic sensors are quite promising
because of high sensitivity & high enough accuracy, ease
of operation and three-dimensional image. Their sensitivity
is in the range of moderate sensitivity (10-5 - 10 -1
mol L-1) based on the analyzed component, design and the
composition of the sensor matrix.
The disadvantage is the cost, still a developing tech-
nology and lack of studies on it impact in different parts of
the human being.
2.3.5 CCD camera full range pH sensor array
CCD camera detection system has many applications in the
fields of science and industry. It has been employed in
many areas of chemical experimentation analysed the
transmitted light through a series of polymer beads that
were derivatized with some complexing agents in micro
machined wells by a CCD camera. Detection of metal ion
species like Ca2?, Ce3?, simultaneous detection of Al(III)
and Fe(III) in alloys by using complexing agent like
chromeazurol S (CAS) (Slim et al. 2007) and determining
simple sugar at different pH value can be achieved using
this method. To extend the measurement range for pH
optodes in (Safavi et al. 2007) the design of an array of five
partially selective reflective optodes for pH measurements
using CCD, the five-different pH optodes were prepared by
coating TY, VB, SC, CR and NB indicators on the mem-
brane. The sensor array was formed from 5 membranes
over a white background. The system was stable over a
period of 40pH measurements over a pH range of 0-14. The
responses of these optodes cover the whole pH range.
123
Microsyst Technol
Fig. 5 Schematic representation of the sensing set-up system (Safavi
et al. 2007)
Frames are taken by the CCD camera and are transferred to
the computer, which were analysed for red, green and blue
components.
Pros & Cons The superiority of this method over previous
reported methods like chemometric for extended pH range is
the flexibility to use computer software for quick analysis
and the MS excel sheet to process data compared to the more
time consuming analysis in conventional spectrophotomet-
ric techniques. They help in very good spatial and temporal
resolution of illuminated areas (Fig. 5).
2.4 Electrical method based pH sensor
2.4.1 Ion sensitive FET pH sensor
ISFET is ion sensitive FET (field effect transistor). ISFET
is an alternate to the glass electrode and is based on the
latest technology (Khan and Lin 2014a, b; Khan et al.
2014a, b). When ISFET is immersed in the solution, the pH
measured is indicated by the current flowing through the
drain terminal. ISFET has smaller size due to latest fabri-
cation technologies and has glass-less shape with powered
pH measurement system (Yuqing et al. 2005). ISFET is
comparatively less expensive vs. glass electrode.
First example pH measurement of a solution can be
performed by amorphous boron carbon nitride (a-BCxNy),
which acts as a sensing membrane in an extended gate FET
(Yuqing et al. 2005). Detection is based on the principle in
which sensing material is applied at gate of ISFET, reac-
tion between the solution and sensing material generates
voltage at gate that causes electric field in channel between
drain and source. The electric field generates the drain
current and this drain current is sensitive to pH. By raising
the carbon contents of a-BCxNy sensing membrane the pH
sensitivity can be increased and can attain a value of
46 mV/pH for concentration of 47% carbon (Yuqing et al.
2005). The sensor response time is close to 6 s. The current
inside the drain terminal indicates the pH that is stable in a
Microsyst Technol
Fig. 6 Ion Sensitive FET Model. Reprinted with permission from
(MICROSENS EPFL Switzerland 2007)
Fig. 7 represents electrical connections of an ISFET device, where D
stands for drain, S stands for source, Sub is substrate and G is
reference electrode called gate. Reprinted with permission from
(MICROSENS EPFL Switzerland 2007)
pH varying solution of phosphate which can be stable over
a period of 10secs.
Second example pH sensing material in this example is
Si3N4. There is another organic ion sensitive membrane
photo polymerized on insulating gate terminal of the sensor
and can be used in measurement of concentration ions like
K?, Ca2? (MICROSENS EPFL Switzerland 2007).
A miniaturized reference electrode Ag/AgC1 is also
realized together with the Ion Sensitive FET chip that acts
as a metal gate electrode to provide a stable reference
Fig. 8 Schematic representation of surface potential. a low and
b high concentration of H? ions. Reprinted with permission from
(Hizawa et al. 2006a)
Fig. 9 Diagram of single pixel for pH image sensor. Reprinted with
permission from (Hizawa et al. 2006a). ID input diode, ICG input
control gate, TG transfer register, FD floating diffusion
potential. pH concentration range is between 1-12 and
sensitivity is about 50 mV/pH (MICROSENS EPFL
Switzerland 2007). Operating temperature range of this
ISFET is from -45 to 120 C while the response time is
less than 1 s. Its stability is about 0.1 pH/day.
The numbers in Fig. 6 can be described as: (1) Drain, (2)
Source, (3) Substrate, (4) Si02 insulator, (5) Si3N4 or
AI203 insulator, (6) Metal connection, (7) Reference
electrode, (8) Ion sensitive membrane, (9) Encapsulant
(Fig. 7).
Pros & Cons ISFET has smaller size due to latest fab-
rication technologies and has glass-less shape with pow-
ered pH measurement system (Yuqing et al. 2005). ISFET
is comparatively less expensive vs. glass electrode.
The disadvantages associated with these sensors is the
drift of the device response over time, which in turn leads
to the poor sensitivity of the device.
2.4.2 Image Sensor based on pH
pH dependent image sensors have various applications
related to industries both in real time and chemical. pH
image sensor works on the principle of charge transfer. The
123

Fig. 10 pH image sensor chip photo (5.1 9 5.1 mm), with a 10 9 10
sensing Array. Reprinted with permission from (Hizawa et al. 2006a)
Fig. 11 The conversion principle from pH to charge. Reprinted with
permission from (Hizawa et al. 2006a)
chemical variations are monitored by the dynamic images
and two dimensional distributions provided by the image
sensors. pH image sensors are fabricated on the CMOS
process technology. pH sensing area of the device contains
three different layers; SiO2 (silicon oxide)/Si3N4 (ion
sensitive membrane)/Silicon substrate of p-type (Hizawa
et al. 2006a). Figure 8 represents an EIS system (elec-
trolyte/insulator/semiconductor system).
Based on Nernst equation chemical potential (uC) is
represented by the following equation (Hizawa et al.
2006a)
uC ¼ VREF þ ðRT=FÞlnaHþ
123
Microsyst Technol
Fig. 12 Conductimetric pH sensor Reprinted with permission (Ku-
mar et al. 2015)
VREF = reference electrode voltage, R is gas constant,
T = absolute temperature, F is Faraday constant and aH?
is hydrogen ion concentration. This equation applies to pH
image sensors and use charge mass transfer technique.
Figure 9 is the circuit diagram for pH imaging sensor. It
also shows a source flower circuit and reset switch with
final chip design (Fig. 10).
Figure 11 describes the sensing potential of a single
pixel. Figure 11a describes the resetting of clock diffusion
to initiate the clock cycle. Figure 11b describes the flow of
electric charge into the potential well under the sensing
region and the input diode potential is reduced. Figure 11c
describes that the input diode is pulsed from VID1 to VID2
and kept again VID1. Figure 11d describes that the transfer
gate is turned on and the charge in the sensing region is
transferred to the floating diffusion region.
Some pH image sensors are based on ISFET (Ion sensitive
field effect transistor). They are an array of ISFETS where
each ISFET is responsible for providing one pixel of data.
Recently pH image sensors use the complementary
metal oxide semiconductor (CMOS) technology which is
faster and best suitable for use in fast industrial
applications.
2.4.3 Conductimetric pH sensor
pH sensor based on conductivity of varied materials and
pH-responsive hydrogel is the base of conductimetric pH
sensors. The conductimetric pH sensors are developed by
coating interdigitated electrode arrays with a hydrogel
membrane that is patterned by photolithography (Ploshin-
skii 1988). The shrinking of the hydrogel sensing layer
causes a response to the analyte under observation which
causes a change in electrical properties. An example of
conductimetric pH sensor is where poly-aniline (PANI) a
pH sensitive and conducting polymer with multiple appli-
cations in pH sensing (Khan et al. 2012) is deposited over
the inter-digitated electrode (IDE) structure. Thick silver
film paste (Heraeus Materials) has also been used as con-
ductive material (Fig. 12).
Microsyst Technol
Fig. 13 Representative drawing of interdigitated microarray elec-
trodes. Reprinted from (Maleki and Safavi 2004) @2007 with
permission from Elsevier
Fig. 14 Schematic diagram of cantilever based pH sensor. Reprinted
with permission from (Bashir and Gupta 2007). 1 bending plate, 2
mechanoelectrical transducer, 3 hydrogel layer, 4 Si plate, 5 socket, 6
tube, 7 interconnect and 8 is solution
2.4.4 Potentiometric pH sensor
The potentiometric pH sensor measures the signal as potential
difference (voltage) between the reference electrode and
working electrode. The potential of working electrode is
dependent on the concentration of analyte in solution or gas
phase. The defined reference potential is provided by the
reference electrode. Several polymers have been considered
for potentiometric pH sensors (Karyakin et al. 1996; Lakard
et al. 2004; Lakard et al. 2005; Kang et al. 1997). For use in
clinical, dermatological and biological applications, such as
in vivo analysis linear polyethylenimine (L-PEI) and linear
polypropylenimine (L-PPI) (two synthetic enzymes and bio-
compatible polymers) films were prepared by electropoly-
merization of three different monomers: ethylenediamine
(EDA), 1,3-diaminopropane (1,3-DAP) and diethylenetri-
amine (DETA). The above polymers are suitable for pH
biosensors because of their strong chemical affinity to the
electrode surface during the step of electroploymerization.
Potentiometric miniature pH sensors based on elec-
trosynthesized polypyrrole films developed by Lakard et al.
have been reported (Lakard et al. 2007). These pH sensors
have two interdigitated microelectrodes where one elec-
trode sensor is coated with polypyrrole film, and the other
one used as reference electrode is coated with silver. It is
shown schematically in Fig. 13.
Pros & Cons Potentiometric pH sensors have fast
response time and are efficient at high pressure and
Fig. 15 Schematic diagram of microcantilever. Reprinted with
permission from (Ji et al. 2001)
Fig. 16 Schematic diagram of magnetoelastic sensor. Reprinted with
permission from (Cai and Grimes 2000)
temperature. It can be used almost universally since it does
not have the disadvantage associated with optical pH sen-
sors. It is one of the most sensitive method of measuring
pH from 0 to 14 and has good repeatability.
2.5 Acoustic pH sensor
2.5.1 Cantilever and microcantilever pH sensor
pH of an aqueous solution is measured by the cantilever pH
sensors. The working principle for a cantilever based pH
sensor is that the cantilever is fixed with a material that has
piezo resistive properties (Bashir and Gupta 2007).
Based on pH, the aqueous solution produces shrinking
or swelling of the hydrogel, which produces deformation in
the cantilever (Fig. 14).
Modified s (SiO2)/(Si3N4) has been used as microcan-
tilever for pH measurement via micromechanical technique
(Ji et al. 2001). Surface modification of the cantilever
creates change that is relative to change in pH causing the
bending of cantilever because of differential surface stress.
Examples of microcantilever based pH sensors are (1)
Aminosilane-modified SiO2/Au that performs robustly
over pH range 2 ± 8 (49 nm detection/pH unit), (2) Si3N4/
Au cantilevers which perform well at pH 2 ± 6 and 8 ± 12
(30 nm detection/pH unit) (Fig. 15).
Pros & Cons Advantages of using microcantilevers
include: their high sensitivity, low cost, low analyte
requirement (in ll), non-hazardous procedure, quick
response.
123

The disadvantage is the deflection resolution which may
be in nm.
2.5.2 Magnetoelastic pH sensor
The working principle of magnetoelastic pH sensor is
based on the interconversion of magnetic and elastic
energies (Cai and Grimes 2000). Electrical field is applied
on drive coil which cause the induction of the magnetic
field. Due to this magnetic field the substrate starts to
vibrate with a certain frequency. Due to change in the pH,
the mass of the pH sensitive material changes, due to
swelling or shrinking of the material, which cause the
change in the frequency of vibration and is detected by the
pickup coil. So, in this way the pH of the material can be
calculated. If the mass increases, the frequency of the
vibration decreases and vice versa.
Fundamental frequency formula is defined by (Hizawa
et al. 2006a):
p wide range of microenvironments as well as prortability and
fr ¼ E=q:1=2L
Where L = length of sensor and E = Young’s modulus.
By changing the mass, the frequency is also changed. So,
the change in the frequency can be measured as:
Df ¼ fr Dm=2mo
where Df is the change in frequency and Dm is change in
mass (Fig. 16).
Pros and Cons of pH sensor The advantage is that it’s a
relative cheap method. The disadvantage is that since the
sensor’s resonance frequency can vary with ambient tem-
perature and earth’s magnetic fields, it will reduce the
accuracy and reliability of measurements.
2.6 Wireless sensor
2.6.1 Wireless pH sensors
Wireless pH sensor based on the use of salt-independent
micro-scale polymer spheres have been reported in (Ruan
et al. 2003). Poly(vinylbenzylchloride-co-2,4,5-tri-
chlorophenyl acrylate) (VBC-TCPA) spheres, approxi-
mately 725 nm in diameter, were prepared by dispersion
polymerization then derivatized with diethanolamine to
realize a mass changing pH-responsive polymer. While the
pH-responsive polymer spheres are suitable for use with
any mass-sensitive sensor platform, in this work, the
polymer spheres are combined with magnetoelastic thick
films to achieve a remote query pH sensor. The magne-
toelastic pH sensors were fabricated by spin-coating the
123
Microsyst Technol
aminated polymer spheres onto the surface of a magne-
toelastic ribbon. The pH response of these sensors was
examined by monitoring changes in sensor resonance fre-
quency as a function of test-solution pH. The sensors
demonstrate a linear pH response from pH 3.0 to 9.0, with a
change in resonance frequency fr of 0.2% fr per pH for a
1.5-lm thick polymer layer. Measurements were virtually
independent of background potassium chloride
concentration.
Pros & Cons The advantage of this sensor is its wireless
and passive nature, that can allow measurement of long-
term pH monitoring in otherwise inaccessible area. The
disadvantage is often the cost competitiveness compared to
wired system.
2.7 Miniaturization of pH sensors
For high resolution and non-destructive microprofiles in a
commercial viability, miniaturization of pH sensors is
important. The miniaturized pH sensors is important for
research applications in environmental sciences, biomedical
sciences, biotechnology, microbiology and food science
(Ruan et al. 2003; Shoukat and Khan 2017a, b, c, d).
Semiconductor industry advances in parallel with novel
polymer based materials have helped to develop pH sensors
where performance can be optimized based on applications.
Novel hydrogel based pH sensors with piezo resistive silicon
has been developed using PVA-PAA (polyvinyl alcohol-
polyacrylic acid) (Khan et al. 2017; Thong et al. 2006;
Korostynska et al. 2007; Santiago et al. 1998). A pH based
sensor that can measure blood plasma ex vivo has been
developed from poly(2-hydroxyethyl methacrylate) and
ionisable 2-(dimethylaminoethyl)methacrylate with an
approximate thickness of 10 lm The above sensor can
measure pH over a period of [40 h and the mechanism of
action is reversible.
Photolithography based pH sensor has been developed
for commercial applications. In this method metal elec-
trodes can be patterned on oxidized silicon surface. The
patterned electrode was coated with polymer. One of the
electrode has polymeric film as coating while the other has
silver coating to be used as reference. When miniaturized,
the sensors can also be used for biomedical applications
such as remote tracking of gastric or esophageal pH on
patients suffering from gastroesophageal reflux disease.
3 Representative pH sensor materials
 S/ Material Detection Physics or Advantages Disadvantages Applications References
No. Method Chemistry

1 N,N0 -bis(4-diaminobenzyliden)-1,2- Optical Absorption Effects of Weight, cost, unfamiliarity, environmental Measurement of strain, Yuqing et al.
cyclohexandiamine fiber and ionic sensitive temperature, pressure (2005), www.
based pH emission strengths are wikipedia.
Microsyst Technol

sensor negligible com)

2 N,N0 -bis(4-diaminobenzyliden)-1,2- Optical Absorption Effects of Weight, cost, unfamiliarity, environmental Measurement of strain, Yuqing et al.
ethanediamine fiber and ionic sensitive temperature, pressure (2005), www.
based pH emission strengths are wikipedia.
sensor negligible com
3 2,6-bis[(4- Optical Absorption Effects of Weight, cost, unfamiliarity, environmental Measurement of strain, Yuqing et al.
dimethylaminopheylimino)ethyl]pyridine fiber and ionic sensitive temperature, pressure (2005), www.
based pH emission strengths are wikipedia.
sensor negligible com
4 Synthesis of Poly(acrylic acid-co-isooctyl Mass Resonance Easy to The swelling of PH responsive polymer is Sensing of biological, Yuqing et al.
acrylate) hydrogel with acrylic acid and sensitive with fabricate affected by the salt concentration of chemical and environmental (2005), Cai
N,N-methylenebis(acrylamide) pH certain and low immersion solution conditions and Grimes
sensor frequency material cost (2000)
5 Pt/PtO2 Metal Adsorption Good Destabilization by physiological and Used to develop a pH Yuqing et al.
oxide pH stability, fast higher concentration of chloride which electrode at high (2005),
sensor response cause dislocation of hydrate oxide film temperature and high O’Hare et al.
pressure (2006)
6 W/W2O3 Metal Adsorption Good Destabilization by physiological and Used to develop a pH Yuqing et al.
oxide pH stability, fast higher concentration of chloride which electrode at high (2005),
sensor response cause dislocation of hydrate oxide film temperature and high O’Hare et al.
pressure (2006)
7 Pb/PbO2 Metal Adsorption Good Destabilization by physiological and Used to develop a pH Yuqing et al.
oxide pH stability, fast higher concentration of chloride which electrode at high (2005),
sensor response cause dislocation of hydrate oxide film temperature and high O’Hare et al.
pressure applications (2006)
8 Ru/RuO2 Metal Adsorption Good Destabilization by physiological and Used to develop a pH Yuqing et al.
oxide pH stability, fast higher concentration of chloride which electrode at high (2005),
sensor response cause dislocation of hydrate oxide film temperature and high O’Hare et al.
pressure (2006)
9 Ir/IrO2 Metal Adsorption Good Destabilization by physiological and Used to develop a pH Yuqing et al.
oxide pH stability, fast higher concentration of chloride which electrode at high (2005),
sensor response cause dislocation of hydrate oxide film temperature and high O’Hare et al.
pressure (2006)

123
 S/ Material Detection Physics or Chemistry Advantages Disadvantages Applications References
No. Method

123
10 Sb/Sb2O3 Metal oxide Adsorption Good stability, fast Destabilization by physiological Used to develop a Yuqing et al. (2005),
pH sensor response and higher concentration of pH electrode at O’Hare et al. (2006)
chloride which cause high temperature
dislocation of hydrate oxide and high pressure
film
11 Poly-m- Conducting Linear response from pH Good potential Complexity of construction, Medical and Yuqing et al. (2005),
phenylenediamine polymer pH 1.5–13 and slope of stability and fragile materials involved, biological Arshak et al. (2007)
sensor 56.7 mV/pH reproducibility frequent calibrations applications
12 Poly(methacrylic Nano- Expansion and reversible Highly sensitive, low Integration of cantilever arrays Biological Yuqing et al. (2005),
acid)(PMAA) with Constructed change in surface stress of power, and compact and microfludic channel applications Stetter et al. (2006),
poly(ethylene glycol) cantilever- micro-cantilever transducers network is still Stetter et al. (2006),
diamethacrylate based pH underdevelopment Boisen and Thundat
sensor (2009)
13 Mercaptohexadecanoic Nano- Changes in interfacial stress Highly sensitive, low Integration of cantilever arrays Semiconductor and Yuqing et al. (2005),
acid (MHA) and Constructed between thiol-covered power, and compact and microfludic channel Integrated circuits Stetter et al. (2006),
hexadecanthiol cantilever- cantilevers and buffer transducers network is still design technology Stetter et al. (2006)
(HDT) based pH solutions of various pH underdevelopment
sensor occur
14 Amorphous boron ISFET based Ion sensitive Improved Difficult to control, varying time Biosensor Yuqing et al. (2005),
carbon nitride (a- pH sensors measurement to time microchip Hizawa et al. (2006b)
BCxNy) stability, rapid applications
response and
accuracy,
Compatible
15 Si3N4 pH image Ion sensitive (Array of Array of ISFET Harder to control, ionic strength Biochemistry and Yuqing et al. (2005),
sensor ISFET) (about 30 pixels per is varying time to time different chemical Hashemi and Mehdi
second), accurate, analysis field (2005), Gillies et al.
compatible and (2004)
stable
Microsyst Technol
Microsyst Technol
4 Conclusions
In this research article, we explored broadly different pH
sensors based on material properties that are used for
varied methods of detection in optical, chemical and bio-
chemical fields as per current state of research. We dis-
cussed physical and chemical properties of various pH
sensing materials in details based on the latest literature
reports and their potential for development of applications
and functionalities in various fields. This review is aimed
to give a basic understanding of the behavior of different
pH sensors, to describe what kind of materials to be used
for different pH sensors, what for sensor properties and
applications can be obtained, and which special features
have to be respected. Suitable material selection and
detection methods are very important. This study will help
the researchers to get an overall holistic view of different
pH detection methods and methods available and enable
them to make a judicious choice based on their needs.
Based on the end-user application requirements along with
selectivity and sensitivity needs, the choice of a polymer,
chemical or method needed for pH measurement can be
decided.
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