Sensing with Phosphor-doped PDMS

F. Sabri*, K. Lynch*, R. Wilson*, S. W. Allison

*U. S. A, Department of Physics, University of Memphis, Memphis, TN., U. S. A., Emerging Measurements, Collierville, TN.
Keywords: Phosphor Thermometry, flexible electronics,
doped PDMS Sensing.

be used as a tool for characterizing, understanding,

diagnosing and improving the host material.

Abstract

In previous work, Aizawa [9] impregnated silicone with ruby

powder. They tested silicone sheets 1 mm thick by 10 mm
diameter with dopant levels of 10, 20, 30, 40, and 50% by
weight. They utilized the fluorescence phase shift approach,
demonstrating a temperature dependent phase shift from -3 to
77 C. The time response to temperature of the underlying
copper block matched that of a Type K thermocouple.

Thermometry with thermographic phosphors usually involves

superficial application of a thin coating to the surface of
interest. In contrast, the subject here concerns a thicker
luminescent target consisting of a flexible phosphor-doped
polymer, from the polydimethylsiloxane (PDMS) family.
The purpose is to produce a flexible attachable/detachable
material which can be used for temperature measurement of
the underlying surface it contacts. PDMS samples loaded
with 1, 5, 15, and 50% of the phosphor La 2 O 2 S:Eu were
fabricated and tested. For all doping levels, detectable and
useful fluorescence signals were readily attained for 365 and
405 nm incident excitation. The PDMS host appeared not to
affect the spectral properties of the incorporated phosphor.
Additional characterization of optical, thermal and
mechanical properties (stress/ strain behavior and temperature
dependent compression response) as a function of dopant
concentration described here validate this as a temperature
sensing material.

Many luminescent material choices are available for

thermometry. Aizawa [9] chose ruby from several other Crdoped materials. Brbach [4] lists over 100 candidate
phosphors that have received attention for phosphor
thermometry. The best choice for a given application
depends on a wide variety of factors. The present work
involves the phosphor La 2 O 2 S:Eu. The deep red emission
from ruby is easily excited in the visible. This contrasts with
La 2 O 2 S:Eu which requires deep blue or near ultraviolet for
efficient excitation where the sources are less bright and more
expensive. However, temperature sensitivity of this Eu-based
phosphor is greater. Emission from the 5D 2 state produces a
number of narrow bands in the blue and green for which the
decay time changes about 5% per C at room temperature.
For ruby it is less than 1%. This brief comparison does not
exhaust the considerations that are required for choosing a
luminescent material for a given application. It is expected
that both of these as well as other phosphor materials should
be scrutinized and examined for future work in this area.

1 Introduction
Luminescence from many phosphors can be exploited for
temperature measurement [1].
Usually this involves
incorporating the fluorescent powder into a coating that is
applied to the surface of interest. For the case of ceramic
phosphors, the coating may be produced using the material
itself by plasma spray, electron beam deposition, etc. In other
instances, the material may be mixed with a binder and
applied as paint. In these examples, the coatings are hard and
thin. This technique has received considerable attention
particularly for high temperature situations such as
encountered in piston and turbine engines [2,3,4].

2 Sample Preparation
Phosphor particles (Phosphor Technology SKL63) were
combined with the prepolymer and crosslinker of Sylgard 184
(Dow Corning) prior to the curing stage of the two-part
elastomer according to the method described previously [8].
Doped samples with weight concentrations of 1, 5, 15, and
50% were prepared in sheets and cut to specific final
geometries appropriate for each characterising method
described below.

In contrast, the subject of the present effort concerns a thicker

luminescent target consisting of a phosphor impregnated
polymer, specifically Sylgard 184 which is from the
polydimethylsiloxane
(PDMS)
family
and
the
characterization of its thermal and mechanical properties.
PDMS is a clear and inert material often used for a wide
variety of situations including optical, biomedical and
aerospace applications [5,6,7,8]. A near term goal is to
produce a flexible material which can be used for temperature
measurement of an underlying surface to which it is attached.
But also, this effort serves the larger goal which is to
investigate how the incorporation of phosphor particles may

3 Stress-Strain Response of Phosphor-Doped

PDMS
Stress-strain behaviour of phosphor-doped Sylgard 184 was
tested under ambient conditions by means of a Mark-10
bench-top tensile tester. Samples were strained at a rate of
50mm/min and results are shown in Figure 1 for the ratios
tested. The highest concentration of phosphor particles (50%)
leads to a compound material with an increased stiffness

compared to lower dopant concentrations where a significant

degree of elasticity can be observed. At 50% concentration a
somewhat linear behaviour is observed while for lower
concentrations classic elastomeric behaviour resembling neat
Sylgard 184 is witnessed. The overall rupture load does not
appear to be significantly dependent on the concentration
amount for the percentages tested here. Stress-strain
behaviour for higher concentrations remains to be
investigated.

T= 100 C

Stress (N/mm2)

T= 25 C
3

1%
5%
15%
50%

0
0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

Strain

Figure 1: Room temperature stress-strain behaviour of

phosphor-doped Sylgard 184.

T=-40 C

Temperature-Dependent Compression Behavior of

Phosphor-Doped PDMS: The samples were placed
individually on an INSTEC mK-1000 temperature control
stage, positioned on the base of a Mark-10 ESM301 tensile
tester. The base temperature was held at a specific
temperature for 10min before compression data was collected
at a rate of 1 mm/min and data collection at a rate of one
measurement per second.. Thermal equilibrium may not have
occurred at the time of data collection. The compression
experiment was manually terminated at a preset value of 8 N.
Figure 2 shows compression responses at three specific
temperatures 100, 25, and -40C. Overall, the family of
curves collected at each temperature suggest that the doped
polymer is less stiff at higher temperatures (100C) and
stiffens significantly at lower temperatures (-40 C) which is
the expected temperature response from the encapsulating
PDMS. Therefore, it is hypothesized that mechanical
response for the concentrations tested here are primarily
dominated by the polymer and not as much by the dopants.
Individual compression-travel curves for each dopant
concentration at
each
temperature
are
however
distinguishable reflecting a temperature sensitive response in
each case.

Figure 2: Compression-travel behaviour of phosphor-doped

PDMS at 100C, 25C, and -40C.

4 Sample Temperature Dependence

The goal of a temperature dependence test was to establish
that luminescence is detectable and produces the
characteristic expected response.
The test arrangement for this is shown in Figure 3 which
illustrates a sample compartment with a Peltier heater/cooler
into which the sample was placed. It was in intimate contact
with a copper plate on the heater/cooler surface and secured
with adhesive taped on its edges. A type K thermocouple was
situated into a small hole in the copper for establishing the

temperature. A Thorlab model M365L2 LED which emits

365 nm was directed at the target. A BNC Model 575
pulse/delay generator provided electrical impulses of 5 to 7
volts to drive the LED. A lens gently focussed the LED
output onto the sample. The fluorescence thus generated
passed through an intervening filter, Andover 510FS10-25.
Its peak transmission at 510 nm and 10 nm width (full width
half maximum) adequately permits several stark components
of the 5D 2 -7F 3 transition to reach the photomultiplier tube
(PMT) for detection, Hamamatsu H5783-01.

Figure 5 depicts a typical fluorescence waveform. There is a

rise time that characterizes the emission. When the pulse
width is sufficiently long, the signal reaches a limiting value.
When the LED terminates, immediately the fluorescence
decreases. The temporal dependence is commonly expressed
as = + ZKHUH  LV WKH GHFD\ WLPH DQG LV D YHU\
sensitive function of temperature. In this case C is a constant
signal that as practice teaches may result from constant
background light, detector noise, electronic direct current
offset or possibly other sources.

Figure 3: Illustration of Sample Compartment.

Figure 4 shows the complete test layout. The PMT output
connected to a Tektronix 2012B digital oscilloscope where a
trigger synchronous with the LED pulse from the pulse
generator triggered the display.

Figure 5: LED-excited fluorescence rise and decay at 9.2 C.

Figure 6 shows the decay portion of several signals acquired
from 9.5 to 54.2 C. It is seen that I 0 is also sensitive to
temperature. This feature is not so pronounced when
illumination is with an excitation pulse of width much less
than the decay time. Overall, the observed temperature
dependence was as expected.

Figure 4: Data acquisition and display block diagram.

The amplitude analog-to-digital conversion resolution of this
Oscilloscope is 8 bits. The digitized signal consists of 2500
data pairs. As visualized by Figure 3, a small patch of dopedPDMS was placed in the compartment. For this temperature
dependence test, the doping level was 50%.

Figure 6: Decay waveforms versus temperature.

5 Phosphor-doped PDMS
Coating Comparison

and

Phosphor

A careful comparison was made of fluorescence from a

phosphor-doped PDMS sample and a thin layer of phosphor
coated onto a copper plate. The latter sample was 15% by
weight and about 2 mm thick. It was placed in the sample
compartment and allowed to equilibrate with ambient
temperature. Eight waveforms were acquired in succession
which were averages of 128 signals. Then these were
subsequently averaged in software, thus improving the signalto-noise. The temperature was 20.6 C. The sample was then
removed so that the phosphor coated surface in the sample
compartment could be illuminated. After about 8 minutes,
the temperature was 20.8 C. The phosphor coating is a
mixture of phosphor and VHT Flameproof SP115 Satin
Clear. This is a high temperature paint, colorless, sold in auto
parts stores. The signal from the coating was initially about a
factor of two higher.
Subsequently the gain on the
photomultiplier detector was adjusted to obtain a signal
approximately the same amplitude as the doped PDMS
sample. This is to eliminate the possibility of a nonlinear
response by the detector. The two signals are shown in
Figure 7.

Figure 8: 15% sample with light emerging

from back of side illuminated at 405 nm.
In order to assess what thicknesses for which wavelengths
may be viable, absorption measurements are of value.
Absorption behaviour in the ultraviolet and visible ranges
were made by means of a scanning Beckman spectrometer
such that prepared samples were placed inside a quartz
cuvette and scanned at a rate of 500nm/min. The pure
phosphor powder was compressed into a quartz cuvette and
scanned separately in order to establish the effect of the
surrounding encapsulating polymer on the absorption/
emission behaviour of the phosphor particles. The results are
shown in Figure 9 and the appearance of bands associated
with La 2 O 2 S:Eu can be clearly seen. Graphs presented
include background subtraction.

Figure 7: Comparison signals from doped PDMS and

phosphor coating.
It is seen that the rise times are slightly different. However,
in this view, the fluorescence decays appears almost identical.
This suggests that the PDMS matrix has little physical or
chemical effect on the phosphor. This is all the more striking
since the phosphors used in the PDMS and the coating were
from different batches. The coating phosphor was Lot #
23015.

Figure 9: Absorption spectrum UV-Vis range.

7 Toroidal Inductor Measurement

An example temperature measurement application was
selected for testing the phosphor-doped PDMS as a
temperature sensor. It involved the surface of the magnet of a
toroidal inductor on a computer motherboard. A thin (1<
1mm) rectangular 5% phosphor-impregnated patch was
attached by tape at its edges. It was considered that the
signal would have been much brighter using the 50% sample.
Since this was already tested earlier, it was thought that using
a more dilute material would be instructive.

6 Absorption Measurements
For all but the thickest sample of 50% doping both 365 nm
and 405 nm produced luminescence that emerged from the
side opposite of illumination, as seen in Figure 8. Thus
temperature may be measured from either side of the material.

For this test demonstration, a 405 nm emitting diode laser

(Star 405F100 from Roithner) was directed onto the phosphor
patch as seen on the bottom frame of Figure 10 bottom shows
this in the test setup. With the room lights off, the top frame
of Figure 10 shows where the laser strikes the inductor. To

the human eye it appears pink since what is seen is both the
diffuse blue from the laser and the longer emission of the
fluorescence that is comprised of many colors. The bottom is
the nearly identical scene with lights on The fiber probe
aimed at the target contains a central fiber that convey the
excitation and it is surrounded by receiving fibers that
transmitted received fluorescence to a PMT detector.. It is
situated about 1 inches from the fluorescing target. The
fluorescing spot is about 3 mm diameter, at least. The laser
was pulsed with a duration of 40s and repetition rate of 10
pulses per second. The applied voltage was 5.5 volts. Full
power, 100 mwatts, is at 6.0 volts according to the
specification sheet. Thus the energy per pulse is estimated to
be a few microjoules per pulse. It should be noted that the
signal is the average of 128 sequential signals, i.e. over about
12.8 seconds.
An ambient reading was acquired one minute before the
power to the computer was switched on. Readings were
taken every minute from 1 to 8 minutes and then less
frequently after that. The temperature rises from about 23 to
37 C. After 10 minutes, the power was turned off. The table
shows temperature versus time. Figure 11 is a plot of T
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determination was taken from a different batch of phosphor
and might deviate slightly from this material. A careful
calibration of this particular sample will be performed later.
The correction of the curve slightly up or down will not affect
the conclusions here.

Figure 11: Measured temperature versus time.

8 Concluding Remarks
The phosphor-doped sensing material is chemically stable and
shows promise as a detachable and reusable temperature
sensor.
The issues of contact resistance, thermal
conductivity, and thermal equilibrium of course need to be
considered in future work. Depending on the application, a
thermal gradient across the material may be a problem or a
feature to exploit for heat flux determination. Another
distinguishing feature of the subject elastomer material is that
it is can be easily stressed and/ or strained incrementally.
Thus, future research will address ways to exploit the
fluorescence to indicate this as well as temperature. The
method described here specifically refers to incorporation of
phosphor particles in Sylgard 184 host but can be easily
applied to other elastomeric and non-elastomeric transparent
encapsulating polymers.
Finally, other material candidates that may incorporate
phosphor materials are aerogels. The authors have some
laboratory tests relating to this to be reported at a future time.

Acknowledgements
S. W. Allison wishes to acknowledge the assistance of his
Emerging Measurements colleagues M. A. Akerman and D.
L. Beshears with the toroidal inductor measurement.

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