June 10, 2008 / Vol. 6, No. 6 / CHINESE OPTICS LETTERS 401
Dissolved oxygen sensor by using Ru-fluorescence indicator
and a U-shaped plastic optical fiber
Fenghong Chu (
ÂÂÂ
ùùù
), Haiwen Cai (
ééé
°°°
©©©
), Ronghui Qu (
YYY
JJJ
), and Zujie Fang (
yyy
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)
Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800
Received November 29, 2007
A dissolved oxygen (DO) sensor b ased on U-shape plastic optical fiber (POF) and dichlorotris (1, 10-
phenanthroline) ruthenium ([Ru(dpp)
3
]
2+
) as an oxygen indicator was described. Fluorescence intensity
and lifetime were measured when the sensor was soaked into a water bath b lasted with air with varied
O
2
/N
2
ratios. The influence of Ru concentration, ann ealing time and U-shaped POF curve radius on
the system sensitivity was also studied. A two-layer model was proposed to analyze the deviation from
linear relation described by Stern-Volmer equation, and to explain the d eviation and t he dependence of the
fluorescence on curvature of U-shape POF. By fitting the experimentally measured sub-linear relation of
τ
0
/τ ratio versus oxygen concentration, the proportion of effectively sensitive layer and the Stern-Volmer
coefficient can be evaluated to be f = 0.59 and K
SV
= 0.61 typically.
OCIS codes: 060.2370, 120.0120, 130.6010.
Measurement of oxygen conce ntration dis solved in wa-
ter is of major importance, especially in medical sens-
ing, environmental monitoring, and agriculture, for de-
termining the oxy gen co ntent of blood and asses sing
the quality of water supplies. Considerable efforts have
been devoted to developing optical a nd electrochemical
methods for the quantitative analysis o f dissolved oxy-
gen (DO). Compared with other kinds of DO senso rs,
optical sensors show some basic advantages, such as im-
munity to exterior electromagnetic field interference, in-
ertness against sample flow rate or stirring speed, no
requirement for a reference electrode, and no O
2
con-
sumption in the measurement. Ruthenium b onded with
phenanthroline group is characterized by strong absorp-
tion in the blue-green region, large Stokes shift (emitting
in the orange/red spectral region), high quantum yield,
long unquenched fluorescence lifetime (on the order of
ms), and higher stability. It has been suggested by many
authors
[1−3]
as a particularly promising DO sensor for
practical applications. In addition the Ru-incorporated
organics are very soluble in typical sol-gel prec ursors
[4]
.
In this paper, we used dichlorotris (1,10-phenanthroline)
ruthenium ([Ru(dpp)
3
]
2+
) as an oxygen indicator, and
plastic optical fiber for delivering the excitation light and
picking up the lo nger wavelength fluorescence radiation.
To enhance exciting efficiency, the POF sensor head was
bent in U-shape. It is found experimentally that the ob-
tained characteristics show deviation from linear relation
described by commonly used Stern-Volmer eq uation. A
two-layer model was proposed to explain the phenomena.
The effect of oxygen indictor concentration, sol-g e l film
annealing time and U-shape POF cur ve radius on the
sensitivity wa s also studied.
Oxygen as a triplet molecule is able to efficiently
quench fluorescence of certain fluorophores . The quench-
ing degree relates to the frequency of collisions between
oxygen and fluorophore molecules, and therefore to the
concentration, pressure and temperature of the media
containing oxygen. The oxygen quenching decrease s not
only the fluorescence intensity, but also the fluorescence
lifetime. It is shown that the ratio of the fluorescence
intensities to lifetimes in absence (I
0
/τ
0
) and presence
(I/τ ) o f oxygen can be described by Stern-Volmer equa-
tion:
I
0
/I = τ
0
/τ = 1 + K
SV
[O], (1)
where K
SV
is Stern-Volmer constant, and [O] is the con-
centration of oxygen, in other words, it is the proportion
of oxygen in the mixed gas.
The lifetime can b e measured by the phase-fluorometry
method, which has a merit of immunity to fluctuation
of the lig ht source and is more reliable than intensity
measuring alone. In the method, the exciting source is
modulated sinusoidal and the phase shift between e xci-
tation and fluorescence is measured in absence (φ
0
) and
presence (φ) of oxygen. The fluorescence lifetime can be
obtained with the relation of tan φ = 2πf τ
[5]
, where f is
the modulation frequency. Then the relation between φ
and [O] can be obtained:
tan φ
0
/ tan φ = 1 + K
SV
[O]. (2)
In the experimental setup, the phase shift is c alculated
by the correlation method
[6]
. Signals of the modulated
exciting light and generated fluorescence are measured
respectively as
x(t) = A sin(2πf t + ϕ
1
) + N
x
(t), (3a)
y(t) = B sin(2πft + ϕ
2
) + N
y
(t), (3b)
where x(t) and y(t) stand for the two signals, A and
B are the amplitudes, N
x
(t) and N
y
(t) are respective
noises, which must be taken into consideration in a prac-
tical measuring system. Correlatio n R
xy
(∆t) betwe en
them can be expressed as
R
xy
(∆t) =
1
T
T
Z
0
[A sin(2πf t + ϕ
1
) + N
x
(t)]
×[B sin(2πf(t + ∆t) + ϕ
2
) + N
y
(t + ∆t)]dt. (4)
1671-7694/2008/060401-04
c
2008 Chinese Opt ics Letters