Sensors and Actuators B 56 Ž1999.

158–163

Highly sensitive hydrogen sensors using palladium coated fiber optics

with exposed cores and evanescent field interactions
a,b,)
Massood Tabib-Azar , Boonsong Sutapun a , Rose Petrick a , Alex Kazemi c

a
Electrical Engineering and Applied Physics Department, Case Western ReserÕe UniÕersity, Rm 517, Glennan Building, 10900 Euclid AÕenue, CleÕeland,
OH 44106, USA
b
Computer Engineering and Science and Macromolecular Science and Physics Departments, Case Western ReserÕe UniÕersity, Glennan Building, 10900
Euclid AÕenue, CleÕeland, OH 44106, USA
c
Boeing, Space and Defense System, EEL V r Delta IV-CBC 5301 Bolsa AÕe, Huntington Beach, CA 92647, USA
Accepted 22 March 1999

Abstract

A novel fiber optic hydrogen sensor which is constructed by depositing palladium over an exposed core region of a multimode fiber is
reported. The sensing mechanism is based on evanescent field interaction with the palladium coating. Since the length, thickness, and
composition of the palladium patch can be controlled independently of each other, it is possible to increase the speed of our sensor at
lower temperatures while maintaining its sensitivity. In micromirror sensors such an optimization is not possible due to a restriction
imposed on their active area of interaction by the fiber optic cross-section. Micromirror fiber optic sensors, studied in the past, take
advantage of the reflectionrabsorption of a palladium film deposited at the end of a fiber resulting in one sensor per fiber optic strand. On
the other hand, many evanescent field-based sensors can be deposited over a single fiber optic strand. Using a 100 A ˚ thick palladium with
1.5 cm interaction length, we could detect hydrogen in the 0.2–0.6% range with corresponding response times of 30–20 s at room
temperature. At y108C, these response times increased by a factor of only 2. q 1999 Elsevier Science S.A. All rights reserved.

Keywords: Hydrogen sensors; Palladium; Fiber optics

1. Introduction of location nor is a real time system. It is also very

Commercial and military launch vehicles are designed
to use hydrogen as a main propellant which is very volatile,
extremely flammable, and highly explosive. Hydrogen gas
detection due to excessive leakage is a great concern at
both the propellant fill ground support equipment ŽGSE.
and within the common booster core ŽCBC. during ground
operation. Current detection systems provide Teflon trans-
fer tubes at a large number of vehicle locations through
which gas samples are drawn and the stream analyzed by a
mass spectrometer. Concern with this approach is the high
cost of mass spectrometer systems, tube routing to and
through the primary booster. The line disconnection at lift
off can also be a major problem in the present approach.
Moreover, the present system does not provide indication
)
Corresponding author. Tel.: q1-216-368-6431; Fax: q1-216-368-
6039; E-mail: mxt7@po.cwru.edu
complex and cumbersome for production and ground sup-
port group personnel.
Fiber optic gas and chemical sensors have been around
for many years and various active and passive optical
sensors have been designed and constructed to detect
hazardous and other gases and chemicals in the past. One
of the important characteristics of fiber optic sensors is
their ability to operate in potentially explosive environ-
ment w1x. They have other important characteristics, such
as simplicity of design and higher sensitivity as well. We
investigated many different and possible types of fiber
optic hydrogen gas sensors to use them as a part of safety
system in rockets. It is projected that as many as a few
hundred cargo-carrying rockets will be deployed per year
during the next few decades to launch various communica-
tion and reconnaissance satellites into the space. To reduce
risk and ensure safety of these operations, hydrogen leaks
should be detected and prevented specially before and
during their launch while they are in the oxygen-rich
ambient of the earth atmosphere.

0925-4005r99r$ - see front matter q 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 9 2 5 - 4 0 0 5 Ž 9 9 . 0 0 1 7 7 - X
 M. Tabib-Azar et al.r Sensors and Actuators B 56 (1999) 158–163
Of the fiber optic hydrogen sensors reported so far in
the literature, the micromirror sensor w2x schematically
shown in Fig. 1a, is probably the most developed one.
Almost invariably, these sensors, as well as the electrical
hydrogen sensors, use palladium as the gas sensitive layer
that when exposed to hydrogen, its electrical and optical
properties change. Micromirror sensor’s structure is quite
simple and it consists of a thin film of palladium evapo-
rated at the cleaved end of a multimode fiber optic as
shown in Fig. 1a. The Pd thickness is in the range of
100–500 A ˚ w2,3x. These sensors are also commercially
available w4x.
Our sensor’s structure, schematically shown in Fig. 1b,
consists of a core-exposed fiber optic where a layer of Pd
is deposited. The light traveling in the fiber, excites decay-
ing, or evanescent fields at the surface of the core ŽFig.
1c.. These fields decay exponentially as a function of
distance in the space adjacent to the fiber’s core. In the
presence of the Pd coating, the evanescent fields are
altered. As the hydrogen is absorbed by the Pd film, it
expands and because of the formation of the palladium-hy-
droxide, both the real and imaginary part of its refractive
index change. The expansion of the Pd film induces a
strain in the fiber and through the elasto-optic effects it
influences the phase of the guided light. The change in the
imaginary part of the refractive index results in a change in
the absorption of the guided light and, hence, it can be
detected by monitoring the light intensity. The change in
the real part of the Pd’s refractive index results in an
effective phase change in the guided light and can be
detected using interferometric techniques.
The sensor structure used here has the following impor-
tant characteristics w5x: Ži. Sensor sensitivity and response
time can be independently optimized at different tempera-
tures. Žii. Potentially, as many as few hundred sensors can
Fig. 1. Ža. Pd micromirror hydrogen sensor. Žb. Evanescent field fiber optic hydrogen sensor. Žc. Evanescent field profile near a core exposed fiber optic
Žnot to scale..
159
be multiplexed on a single fiber optic link w5x. Žiii. It can
detect hydrogen with a wide range of concentrations from
parts per million to few percent. Živ. Its operation tempera-
ture can be designed to cover a wide range from y408C to
q2008C w5x. In Section 2 we discuss the optical properties
of thin-film palladium and dependence of these properties
on the hydrogen.
2. Properties of Pd films
In Fig. 2a we show a normalized transmission spectra
of 100 A ˚ palladium film with and without H 2 present in
the film. Fig. 2b shows the complex refractive index of
palladium Ž n s n q ik . as a function of wavelength w6x. It
is clear that as the hydrogen is absorbed by the palladium
its transmission changes and since the sum of the transmis-
sion, reflection and absorption is unity, the formation of
PdH x results in changes in all of these quantities. It is
postulated that nearly 100% of H 2 is dissociated upon
arrival at the Pd surface and the hydrogen molecules is
converted to two atomic hydrogen w7x. The atomic hydro-
gen then diffuses into the Pd converting Pd to PdH x which
has different optical properties than Pd. Formation of
PdH x also changes the workfunction of the Pd and can be
used in electrical hydrogen sensors in conjunction with
field-effect transistors or as a part of a Schottky diodes
The formation of PdH x also increases the resistivity of the
Pd film. Resistive Pd hydrogen sensors are used in the
past.
The palladium hydride film, PdH x , has two solid phases:
a and b phases, depending upon the PdrH composition.
The reversible a-phase is found at a low hydrogen concen-
tration. As the hydrogen concentration increases, Pd is
transformed to the b-phase. The hydrogen concentration at
160 M. Tabib-Azar et al.r Sensors and Actuators B 56 (1999) 158–163
Fig. 2. Ža. Normalized transmission spectra of a 10 nm Pd film with and
without hydrogen. The difference between these two spectra shows peaks
at 920 nm and at 850 nm. Žb. Refractive indices of bulk Pd as a function
of wavelength w6x. Thin film properties may be different than the bulk
properties.
which the phase transition takes place depends on the film
thickness and temperature and it introduces a hysteresis in
the optical and mechanical parameters of the palladium
film. Transition from the a-phase to the b-phase for a thin
˚
Pd film Ž100 A–1000 A˚ . occurs at a wider hydrogen
concentration range than the transition in the thicker Pd
films Ž) 10 mm. which occurs around 4% H 2 . For hydro-
gen sensing applications, it is highly desirable that the
phase transition in the palladium film to be prevented. This
can be accomplished by either keeping the hydrogen con-
centration low or by using an alloy of Pd with silver or
chromium. These alloys are known to suppress the a to b
transition in Pd over a wide range of hydrogen concentra-
tions. In electrical Pd hydrogen sensors, a heater is usually
used to locally heat the b-Pd and convert it to a-Pd.
3. Evanescent field fiber optic sensor structure
An evanescent field, created when total internal reflec-
tion between two dielectric media occurs, is an electro-
magnetic field in the lower refractive index medium as
schematically shown in Fig. 1c. In the case of fiber optics,
the evanescent field decays exponentially away from the
fiber corercladding interface. Evanescent field based fiber
optic sensors have been widely used in chemical and
biomedical applications w8x. Most of the evanescent-field
based sensors can be divided into two categories; Ž1. The
cladding is used as a sensing material. When exposed to
the environment, optical properties, such as absorption and
refractive index, of the cladding are modified. Ž2. The
cladding is nearly or totally etched away. In this case, the
air acts as the cladding and an external object can be
brought close to the core modifying the evanescent fields
and changing the parameters of the guided light. The
magnitude of interaction depends on optical properties of
the object and the distance between the fiber core and the
object. An example, is a fiber optic pressure sensor that
uses a silicon diaphragm and an exposed-core fiber optic
reported in Ref. w9x.
In the structure shown in Fig. 3, a thin film of Pd,
which is used as a sensing material for hydrogen, is coated
directly onto the core of a multimode silica fiber with 50
mm diameter core and 125 mm total diameter. To expose
the core, the polymer jacket of the fiber optic was manu-
ally stripped off and cleaned with acetone. Then the
cladding was etched using HF and buffered HF for 10–15
min. The total diameter after etching was less than 50 nm.
Subsequently, a thermal evaporator was used to deposition
Pd on one side of the etched fiber. Pd thickness was
monitored using a quartz-crystal monitor during the evapo-
ration. Pd film thickness typically varied from 10–100 nm.
After coating with Pd, some of the samples were notice-
ably bent due to residual film stress. Handling these deli-
cate fibers demanded a lot of care and patience. A metallic
Fig. 3. Photograph of the fiber optic sample holder used to facilitate
handling the fiber optic while etching its cladding and to prevent the
fragile 50–100 mm core region from breaking during the etching process
and subsequent handling.
 M. Tabib-Azar et al.r Sensors and Actuators B 56 (1999) 158–163 161

Fig. 4. Ža. Package structure. Žb. Micro-photograph of the fabricated

silicon micromachined package and the fiber optic inserted through the
v-grooves.

frame that supported the two arms of the fiber was at-
tached to the fiber using shrink tubes as shown in Fig. 3b.
This frame prevented the destruction of the exposed core
region during the palladium deposition and subsequent
handling of the fiber. We are currently considering a larger
core fiber with 100–200 mm diameter with a polymer
Fig. 6. Ža. Sensor output for 0.6% hydrogen in nitrogen as a function of
time. Žb. Sensor output for 0.2% hydrogen in nitrogen as a function of
time. The sample was one-side coated with a 10-nm-thick Pd and had an
active length of 1.5 cm. The measurement was done at room temperature.
The total flow rate was 2165 ccrmin. Žc. The amplitude of the sensor’s
output as a function of hydrogen concentration.

Fig. 5. Experimental set-up to measure the sensor’s output as a function of hydrogen concentration and temperature.
162 M. Tabib-Azar et al.r Sensors and Actuators B 56 (1999) 158–163
Fig. 7. Sensor output at low temperature Žy108C. as a function of time,
using the same sample as in Fig. 5. The dashed line shows temperature
readings in side the gas cell.
cladding. This type of fiber is easier to carry and elimi-
nates the HF etching step.
Packaging the fiber optic hydrogen sensor for a use in
space vehicle, where dimensions, weight, and cost are
critical, is quite challenging. We have started developing a
silicon micromachined structure package as shown in Fig.
4a. It consists of a silicon diaphragm with holes to let the
hydrogen to diffuse into the fiber. The fiber optic sensor in
this package is held underneath the diaphragm through
v-grooves formed using anisotropic chemical etching of
the silicon. This structure can be batch fabricated using
micromachining and wafer-to-wafer bonding technologies
w1x. Fig. 4b shows how tightly the fiber optic fits into a
v-groove.
Fig. 8. Optical ray traces of the guided light and its interaction with the palladium film deposited over the exposed fiber optic core region.
4. Experimental results and analysis
The test set-up for the evanescent filed sensors con-
sisted of the following parts as shown in Fig. 5: a gas cell
with a cooling system, a monochromator, a photodetector,
a gas flow control system, a lock-in amplifier and a
computer to perform data acquisition and analysis. A
double-jacket glass tube was used as a gas cell with gas
mixture flowing into the inner shell and liquid nitrogen
flowing into the outer shell for cooling. A mixture of
hydrogen and nitrogen gases was mixed homogeneously
before flowing into the gas cell. Flow rates of both gases
were individually controlled using flow meters. The mono-
chromator was used to perform spectroscopy and deter-
mine the range of wavelengths where the sensor had the
best sensitivities. A chopper along with a lock-in amplifier
were used to perform synchronous detection of the trans-
mitted light detected using a photomultiplier. Microscope
objectives were used to focus light into the fiber and the
entire experiment and data acquisition and analysis were
performed using a computer. A 650-nm light was used in
fixed-wavelength measurements.
Fig. 6a and b show sensor outputs at room temperature
as a function of time for two partial hydrogen concentra-
tions of 0.6% and 0.2%, respectively. The fiber was coated
in one-side with a 10 nm Pd film. The film thickness, in
this case, was not uniform over the perimeter of the fiber
and the sensor had an active length of 1.5 cm. As shown in
Fig. 6, the sensor showed a good sensitivity and repro-
ducibility with absorption time responses of 20 s and 30 s
for 0.6% and 0.2% hydrogen concentration, respectively. It
 M. Tabib-Azar et al.r Sensors and Actuators B 56 (1999) 158–163
should be noted that the sensor output increased as a
function of hydrogen concentrations from 0.2%–0.6% as
shown in Fig. 6c.
Fig. 7 shows the sensor output at a low temperature
Žy108C. as a function of time, using the same sample as
in Fig. 6. Absorption time response at low temperature is
about twice of that at room temperature. As can be seen in
Fig. 7, the second cycle had lower output and slower time
response which may be due to the low operating tempera-
ture and humidity. Long-term reproducibility of the sensor
at low temperature is subjected to future studies.
The following qualitative model can be used to explain
the increase in the sensor output as a function of hydrogen
absorption in the Pd film. As shown in Fig. 8, the Pd film
has a higher refractive index than the silica core Ž n Pd s 1.80
at 650 nm, see Fig. 2b., but since its thickness is much
smaller than the optical wavelength, it cannot support
traveling optical modes. The contribution of the palladium
is mainly through the imaginary part of its refractive index
which diminishes as hydrogen is absorbed. As hydrogen is
absorbed in Pd, palladium hydroxide is formed increasing
the resistivity of the film. The increase in the resistivity of
the palladium film as a function of hydrogen absorption is
exploited in electrical hydrogen sensors and it is well
known. The imaginary part of the refractive index in
materials is directly related to the free carrier absorption
process and it decreases as the conductivity is reduced.
The real part of the refractive index also changes as PdH x
is formed. It is well known that in most cases the real part
of the refractive index becomes larger as the free carrier
concentration is reduced. This is a stiffening process of the
optical processed in conductors and it is also well known.
The reduction in the imaginary part of the refractive
index of Pd as PdH x forms, explains the behaviour of our
sensor. There are other interesting processes that occur in
the fiber optic in the presence of the non-uniform Pd layer.
As shown in Fig. 8, ridge waveguides form underneath the
Pd layer which result in the redistribution of the light
intensity. This process increases the interaction of guided
light with the Pd film.
Other interaction mechanisms contribute to the sensor
output as well. As PdH x forms, the Pd film expands
resulting in a residual strain inside the fiber. Mechanical
strain reduces the real part of the refractive index, the
163
so-called ‘elasto-optic’ effect w10x, resulting in a change in
the effective reflection of the light from the Pd layer.
Surface roughness of the fiber core due to HF etching
could create light scattering which also affects the sensor
output. These parameters are currently being investigated
in our group and will be published in the future.
5. Conclusion
In summary, we have reported a novel fiber optics
hydrogen sensor which takes advantage of evanescent
interaction of fields at the surface of a fiber optic core and
a palladium film. In our sensor, the interaction length and
the Pd film thickness can be controlled independently.
Hence, the sensor sensitivity and response time can be
independently optimized. Such a control is necessary in
designing highly sensitive hydrogen sensors for low tem-
perature operations with reasonably fast response times. In
contrast, in the micromirror sensors reported in the litera-
ture, the sensitivity and response time cannot be indepen-
dently controlled.
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