Copyright © 2009 American Scientific Publishers Journal of

All rights reserved Nanoscience and Nanotechnology

Printed in the United States of America Vol. 9, 6299–6306, 2009

Nanotextured Organic Light Emitting

Diode Based Chemical Sensor
Sandeep Devabhaktuni1 and Shalini Prasad1
2
∗
1
Department of Electrical and Computer Engineering, Portland State University, Portland, OR-97201, USA
2
Department of Electrical Engineering, Arizona State University, Tempe, AZ 85287, USA

In this paper we present the design, fabrication and development of an optical, label free chemical

RESEARCH ARTICLE
sensor technology based on the portable “lab-on-a-chip” format. This sensor technology employs
the use of nanotextured thin film surfaces packaged in a stacked vertical array format functioning as
organic light emitting diodes (OLED’s). The intensity of emitted light from OLED’s is modulated as
a function of the analyte concentration. The OLEDs were fabricated in a layer by layer configuration
with an indium tin oxide anode and an aluminum cathode and TPD as a hole transport layer and
AlQ3 as an electron transport layer. ITO/TPD/AlQ3 /Al sandwich OLEDs were converted into sensors
by converting the cathode (Al) surface into an active sensing area. The prototype sensor perfor-
mance was evaluated in the detection of two aliphatic hydrocarbons-ethanol and methanol. The
detection sensitivity was found to be in the lower parts per million (ppm). The limit of detection for
ethanol was 1 ppm and that for methanol was 10 ppm. Chemical detection was achieved upon the
comparison of turn-on voltages and the intensities of the output light from the OLED when chemical
was being injected onto the cathode surface, with that of a standard OLED turn-on voltage and
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two parameters to: McMaster
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to the standard was determined as
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Keywords: Optoelectronic Chemical Sensor, Aliphatic Hydrocarbon Detection, Organic LED.

1. INTRODUCTION Tang and Van Slyke2 reported a multi layered organic

Electroluminescent devices using organic materials have
been developed since the 1950’s. Over the last half a
century organic thin films have been packaged in vary-
ing configurations in the sandwich format to develop light
emitting devices. Bernanose, was the first to demonstrate
light generation by applying high alternating current volt-
ages to thin organic crystalline films of acridine orange
and quinacrine.1 The development of these organic lumi-
nescent devices was not suitable for practical device appli-
cations because of the high voltages required to drive the
charge carriers into the organic crystal. In order to obtain
significant light, voltages in the range of 30 V–100 V
were required to drive the device.2 The structure of these
organic luminescent LED’s comprised of thin films of
organic materials like anthracene.3 The power output effi-
ciency of these devices was quite low in the range of 0.1%
to 0.05%. In addition due to lack of long-term stability
of these devices they were not appropriate for commercial
applications.2
∗
Author to whom correspondence should be addressed.
light emitting diode (OLED), which worked, on low oper-
ating voltages with improved performance parameters.
These devices consisted of an organic layer, which was
a sandwich of two organic films. These organic materials
were mono-transport layers i.e., they transported either the
negative charges (electrons) or the positive charges (holes)
and their morphological, recombination and luminescent
properties were chosen such that they were compatible
for the device construction and operation. In addition low
work function alloys comprising of materials such as such
as magnesium and silver were used to inject electrons
and improve the device efficiency. Since then organic
light emitting diodes (OLED) have been of great inter-
est because most of the organic materials that have been
used as layers of thin films stacked on to each other have
demonstrated extremely high fluorescent efficiency in the
whole visible spectrum, color versatility, high brightness,
wide angular emission profile and are of light weight.
This has made them extremely suitable for application in
portable multi-color flat panel displays.4
Recently, there have been different types of organic
luminescent devices using polymers that are known as

J. Nanosci. Nanotechnol. 2009, Vol. 9, No. 11 1533-4880/2009/9/6299/008 doi:10.1166/jnn.2009.1354 6299

 Nanotextured Organic Light Emitting Diode Based Chemical Sensor
polymer light-emitting diodes (PLED),5 which have been
fabricated using a thin film of conductive polymers that
emit light when the device is biased. The device active
area i.e., the regions from which light emission occurs
has been micro structured through micro contact print-
ing or ink jet printing techniques in order to improve the
emission efficiency.6 Polymers with derivatives of poly
(p-phenylene vinylene) and poly(fluorene) have been used
as conductive polymers that emit and absorb electrons
respectively, forming the n-type and p-type layers of the
device.7 These devices utilize the improved surface area
to volume offered by surface texturing to improve the
device performance metrics through controlled layer-by
layer deposition. These devices can be fabricated on rigid
as well as flexible substrates, making those robust.5 8
Other types of OLEDs that have been recently devel-
RESEARCH ARTICLE
oped such as the transparent organic light-emitting device
(TOLED) and stacked OLED (SOLED)9 10 have incor-
porated the advances in nanomaterial technology towards
improving the device performance metrics. These include
the incorporation of nanomaterial composites as well the
use of hybrid organic and inorganic material. The inor-
ganic materials include homogeneous as well as hetero-
geneous conducting as well as semiconducting material
with varying geometries such as nanowires, nanotubes,
nanospheres and other morphologies.11–13 These hybrids
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which in turn improve the device IP: 117.253.107.242 On: Fri, 23 Oct 2015 12:52:32 glass substrate of size 2.5 cm ×
performance metrics
Copyright: American Scientific
by multiple factors as compared to the micro structured
OLED devices.
TOLEDs’ consist of transparent electrodes which can
be used for anode or cathode or even both the electrodes.
TOLED’s have been used in order to improve contrast and
viewing angles of the display systems. SOLEDs’ consist
of vertically stacked transparent OLED’s. These have been
typically used for improved color characteristics and also
for improved resolution14–17
Finally, most recently there have been investigations
in employing OLEDs’ that have been typically used for
light emitting displays towards developing optical sensors.
Kopelman et al., have demonstrated the development of
bio-chemical sensors using OLED technology. Glucose as
well as oxygen has been detected at parts per million con-
centrations using this technique.18
In this paper we have designed and developed a multi
stacked organic light emitting device by identifying the
appropriate combination of organic polymers and anode
and cathode material for achieving the most suitable device
characteristics-reduced turn on voltage for the purpose
of chemical sensing. The device employs the nano tex-
turing in thin films to demonstrate measurable changes
to the turn on voltage and light intensity as a function
of the chemical concentration. The organic light emitting
diode structure selected for this application consists of a
stack of a metal oxide and metal sandwiching two electro
6300
Devabhaktuni and Prasad
active polymers-that function as electron and hole trans-
port layers respectively, with the following multi-stack
configuration-ITO/TPD/AlQ3 /Al.
We have tested the device prototype in detecting
two specific simple aliphatic hydrocarbons in the liq-
uid state-ethanol and methanol. We have demonstrated
lower parts-per-million sensitivity, in detecting these two
hydrocarbons. The key innovation associated with this
chemical sensor technology is the fact that while the detec-
tion of the chemical agent is visual due to the change in
the intensity of emitted light from the electroluminescent
device, the sensor technology is label-free. This indicates
that the chemical agents that have been detected (aliphatic
hydrocarbons) have not been tagged with a fluorescent
tag or an external chemical to make them luminescent.
The chemical agents in their intrinsic form modulate the
intensity of emitted light. The device prototype that we
have tested demonstrates potential towards developing a
label-free, cost-effective, rapid, portable chemical sensor
technology.
2. MATERIALS AND METHODS
2.1. Design of the Base Device Substrate
The multi-stacked OLED was assembled on the anodic
indium
McMaster substrate. The OLED’s were fab-
University
ricated on an ITO coated
2.5 cm. Publishers
Each glass substrate had 3 OLED’s which were
fabricated using a single mask. The process flow is shown
in Figures 1(A–D) and the mask schematic is shown
in Figure 1(E). The mask comprised of rectangular perfo-
rations on an optically transparent plastic. The dimension
of each perforation was 2 cm × 0.64 cm. The mask was
then fixed on to the ITO glass substrate for depositions
of the various organic material layers for developing the
multi-layer stack of the organic polymers. The mask was
removed once the Al cathode was deposited.
2.2. Optimal Fabrication of the OLED
(ITO/TPD/AlQ3 /Al) Multilayer Structure
The process flow for the fabrication of the OLED
chemical sensor utilized the standard photolithogra-
phy techniques. The substrate was glass coated with
Indium-Tin-Oxide (ITO) of thickness 100 nm with a
sheet resistance of 20–30 /m2 (Sigma Aldrich Co,
St Louis, MO). The glass substrate was cleaned with iso-
propyl alcohol and DI water. TPD (N -N 8-diphenyl-N -
N 8bis∼3-methylphenyl1-18-biphenyl-4-48-diamine) and
AlQ3 (tris-8-hydroxy quinoline aluminum) (Sigma Aldrich
Co, St Louis, MO) of thickness about 300 nm were
deposited over ITO to generate a nano textured interface
between the anode and cathode by the polymeric interface
between TPD and AlQ3 . The layers had a two step depo-
sition process. First TPD was deposited onto ITO by the
J. Nanosci. Nanotechnol. 9, 6299–6306, 2009
Devabhaktuni and Prasad Nanotextured Organic Light Emitting Diode Based Chemical Sensor

was deposited on top of the ITO anode andAlQ3 was

deposited over the TPD layer. TPD functioned as the con-
ductive polymer because the holes that were emitted from
anode got stacked in this layer, also in organic materials
holes are more mobile than electrons, so due to the electro-
(B)
(A) static forces between the charge carries holes moved from
TPD layer and are identified to be the conductive layer.
AlQ3 functioned as an emissive polymer that generated
electrons, as the recombination took place in this region at
the junction/interface of the AlQ3 polymer.

2.3. Device Assembly

(C) (D) Using silver epoxy the connections from the power supply
were made to the OLED. The lead contacts were robust
and adhered well on to the smooth surfaces of anode and

RESEARCH ARTICLE
cathode respectively. The epoxy was allowed to dry for a
few hours and the contact leads were taken out from the
epoxy and connected to the positive and negative termi-
Height: 1.43”
nals of a DC voltage supply connected to the supply. This
Width: 1.63’’
resulted in the emission of light from the Al cathode as
(F) demonstrated in Figures 2(A–C).

(E) 2.4. Principle of Operation

The sensing mechanism is based on the measurable vari-
50 µm ation to light intensity due to the effects of the specific
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(G)
Copyright: chemicalPublishers
American Scientific species with a metallic cathode results in the
Fig. 1. (A–D) Schematic representation of the various stages of the pro- modulation of the charge transfer characteristics within the
cess flow of the layer by layer deposition of the various layers of the vertical stack resulting in the modulation of the observable
OLED device. (E) schematic representation of the mask used for device intensity of the emitted light. A specific change to the turn-
fabrication resulting in the formation of 3 OLED devices on a single sub- on voltage and the intensity of emitted light was observed
strate platform. (F) Optical micrograph demonstrating the OLED devices for the two chemicals. The integration of these two aspects
fabricated through the layer by layer process flow. (G) Scanning electron
micrograph demonstrating the nanotexturing of the organic layer inter-
results in the development of the “optical signature” for
face i.e., the interface between the P and N layer formed at the junction the identification of individual chemicals.
of TPD and AlQ3 . The OLED functioned as a chemical sensor by for-
ward biasing the device, with the anode being connected
to the positive terminal of the power supply with respect
two step deposition process. The first step involved ther- to cathode. This causes a stream of electrons to flow from
mal vacuum deposition from tungsten boats at a pressure the cathode towards the anode. So, the emissive layer
of about 105 Torr, with a deposition rate of about 0.2 nm/s. is accumulated at the interface of the two organic poly-
and the formation of a 200 nm thick smooth layer of the mer layers with electrons from the cathode. Simultane-
polymer. The second step involved the drop coating of the ously, due to the positive bias, the anode supplies holes
polymer resulting in a roughened end surface of approx- to the conductive layer. As the voltage is increased the
imately 100 nm. The same process was repeated in the emissive and the conductive layers are accumulated with
reverse order for the second polymer AlQ3 . This resulted electrons and holes respectively. The electrostatic forces
in a nanotextured polymer stack as shown in Figure 1(G). between the electrons and holes make them get attracted
Aluminum was then deposited on top of AlQ3 with towards each other resulting in recombination, releasing
a thickness 1000 nm using thermal vacuum deposition energy in the form of visible light. Since the holes are
(Fig. 1(D)). These materials are selected since; they can be more mobile in organic materials the recombination takes
deposited using the same thermal vacuum deposition with place in the emissive layer. This device cannot be oper-
out disturbing the structure of the diode. ITO functioned as ated in reverse bias because the layers only allow mono
the anode and Al functioned as the cathode, with organic transport. Here TPD acts as Hole Transport Layer (HTL),
polymer layers sandwiched in between them. These were which means it allows the holes to pass through it, but will
the TPD/AlQ3 layers of polymer in the multi stack. TPD block the electrons. So, the electrons from the emissive

J. Nanosci. Nanotechnol. 9, 6299–6306, 2009 6301

 Nanotextured Organic Light Emitting Diode Based Chemical Sensor Devabhaktuni and Prasad

Height: 2.32” Height: 2.56”

Width: 2.75’’ Width: 3.19’’

(A) (B) (C)

RESEARCH ARTICLE

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(D)

Fig. 2. (A) schematic representation of the multi layer nano textured stack of the OLED device (B–C) Optical micrograph demonstrating the func-
tioning of the electroluminescent OLED device. (D) Schematic representation of the measurement circuit comprising of an oscilloscope coupled to a
photo diode circuit connected to the powered OLED that converts the output optical intensity from the OLED into a voltage signal.

layer are at the nano textured interface of the two organic
layers. It is thought that the nano texturing may enhance
the charge retention at the interface. This may be the
reason for observing longer durations of recombination’s
occurring at the interface of conductive (P ) and emis-
sive (N ) layers as compared to standard smooth thin film
OLEDs.
When the chemical is added to the cathode of the
OLED, the applied bias voltage ionizes the chemical
depending ionization potential of the chemical. Conse-
quently, there are no electrons available in emissive layer
for the holes to recombine and release energy initially.
As a result, when there is a change in the concentration
of the specific chemical, there is a change in the elec-
tron concentration moving into emissive layer. This pro-
duces a change in the observed intensity of emitted light.
In addition due to different ionization rates for the two
hydrocarbons, the turn-on voltage accordingly changes.
Figure 3 is the energy band diagram that shows the opera-
tion of the OLED in the normal light emission mode. The
addition of the chemical perturbs the band height of the
homo layer by pushing it don or pulling it up based on
the ionization potentials of the chemicals that are tested,
which in turn changes the threshold turn-on voltage for the
device.
2.5. Measurement Set-Up
The characterization of the OLED chemical sensor was
done by measuring the electroluminescent intensity of the
device in the absence and in the presence of the hydrocar-
bons (ethanol and methanol). This was achieved by using

6302 J. Nanosci. Nanotechnol. 9, 6299–6306, 2009

Devabhaktuni and Prasad Nanotextured Organic Light Emitting Diode Based Chemical Sensor

(A) Intensity of OLED

× 103
6

Output voltage (mV)

5
4
3
2
1
0
0 1 2 3 4 5 6 7 8 9
–1
Input voltage (V)

(B) Intensity of OLED with DI-water

× 103
6

Ouput voltage (mV)

5
4 ____ OLED
____ DI-water
3
2
5.25 V
1

Fig. 3. Energy band diagram of the nano textured multi stacked demon-
strating the HOMO and LUMO layers and the transport of the charge
carriers through the nanotextured multi stack.
a measurement set-up consisting of a photo diode and an
oscilloscope as shown in Figure 2(D). Input voltage was
applied to the device using a direct current supply source.
Increasing the input voltage increased the intensity of the
emitted light, which was measured using an oscilloscope
and a photo diode. The photo-diode
Delivered by converted the light
Publishing
Technology
energy into electrical energy thatIP:was On: Fri,output
in turn read by the
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oscilloscope. The change in the emittedCopyright: American
light intensity was Scientific
recorded for the two hydrocarbons over a range of con-
centrations. They range in between 1000 ppm to 10 ppm
for methanol and 1000 ppm to 1 ppm for ethanol.
3. RESULTS
The multi-layer vertical stacked OLED device character-
istics when functioning in the normal light emitting mode
were determined, as these provided the initial base line
measurements also known as control measurements. In
the next step the device characteristics was evaluated for
the two hydrocarbons-ethanol and methanol for various
concentrations from 1000 ppm to 1 ppm and 1000 ppm
to 10 ppm respectively. Each data point was obtained in
triplicate.
3.1. Baseline Intensity Measurement of OLED
Voltage measurements of the OLED intensity were taken
by using the set-up shown in Figure 2(D). The OLED was
supplied with a step wise increasing input voltage and the
luminous intensity also increased proportionally due to an
increase in the recombination rate of the charge carriers.
The intensity of emitted light from OLED was converted
into a proportional electrical voltage using a photodiode.
A change in the electron–hole recombination at the input
RESEARCH ARTICLE
0
0 1 2 3 4 5 6 7 8 9
–1
Input voltage (V)
Fig. 4. (A) Graph showing OLED turn-on voltage and intensity in terms
of output voltage by conversion through the photodiode. The turn on
voltage is 4.5 V. The light intensity was converted into an electrical volt-
age signal and the output voltage for the input turn on voltage is 38 mV.
(B) Graph showing the intensity of OLED in presence of DI water. There
is an observed shift in the turn-on voltage from 4.5 V to 5.25 V from
the baseline control value which is attributed to the ionization potential
of DI water that is 12.85 eV.
changed
the intensity
to: McMaster of the OLED as a result a change in
University
23 Octvoltage
2015 was observed.
12:52:32
FigurePublishers
4(A) shows the intensity of OLED at different
bias voltages. The measurements were done on three dif-
ferent OLED’s and the graph shows the average values of
the intensities. The turn-on voltage of the device was iden-
tified to be 4.5 V (the point at which recombinations start);
the output voltage shown in the graph is the measure of
intensity of light in terms of voltage using photo diode.
The exponential rise in the current was due to increase
in the number charge carriers and recombinations with
increase in bias voltage.
3.2. Control Measurements of OLED Intensity
3.2.1. OLED Intensity with De-Ionized Water
The OLED was first tuned with de-ionized water in order
to test the sensitivity and control of the device. In addi-
tion the various aliquots of the varying concentrations
of the hydrocarbons were prepared in de-ionized water
(DI), hence it was crucial to determine the baseline device
characteristics due to DI water. In this case DI water
was injected on the metal cathode (Al) surface, of the
OLED. The bias voltage was applied to OLED once
water was injected on to the surface. Again the intensity
measurements were taken with increasing input voltage.
The Figure 4(B) shows the intensity graph of OLED with
DI water. We observed a shift in output light intensity,
which we hypothesize, was due to the loss of ions from

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 Nanotextured Organic Light Emitting Diode Based Chemical Sensor Devabhaktuni and Prasad

cathode due to the polar nature of water. The applied bias
voltage is used for ionization of water molecules, whose
ionization potential is 12.58 eV.19 There is a shift in turn-
on voltage to 5.25 V with a difference of 0.75 V.
3.3. Detection of the Aliphatic Hydrocarbons
Using the OLED Sensor
3.3.1. Methanol Detection
A specific concentration of methanol was injected onto
the Al cathode surface. The volume of test sample dis-
persed onto the cathode surface was 10 l. After 5 minutes
of incubation at room temperature, the turn-on intensity
was determined. Intensity of OLED with presence of the
methanol is shown in Figure 5(A). The presence of the
RESEARCH ARTICLE
than that observed for DI water and second, there was an
observable change in the intensity of emitted light. The
intensity variations were correlated to a voltage change
from 30 mV to 700 mV over the concentration range
from 10 ppm to 1000 ppm as shown in Figure 5(B). The
increase in output voltage correlated to an increase in the
output light intensity with an increasing concentration of
the chemical. The linear dynamic range of detection for
methanol was identified to be between 1000 ppm and
10 ppm. With a decrease in ionization potential there was
a decrease in the threshold turn-on voltage, as observed
from DI water to methanol (5.25 V for DI water and 5 V
for methanol).
3.3.2. Ethanol Detection

hydrocarbon altered the intensity of the OLED from its Similar to that of methanol, ethanol of 10 l volume was
normal emission intensity. The change in the turn-on volt- injected onto the cathode surface. Intensity of OLED with
age from baseline to methanol was identified to be 0.5 V presence of the Ethanol is shown in Figure 6(A). The pres-
from the control measurements of an OLED operating in ence of the ethanol altered the intensity of the OLED from
the normal mode. The change in the bias voltage was its standard intensity while operating under normal condi-
attributed to the ionization potential of methanol, which is tion. The intensity variations due to the effect of ethanol
10.85 eV.20 The ionization potential was smaller than that over the concentration range from 1 ppm to 1000 ppm,
of DI water. As a result of which the charge carriers in the which was the linear dynamic range of detection, corre-
conductive region changed, which in turn modulated the lated to an output voltage change from 50 mV to 800 mV
energy band diagram by pulling down the HOMO level as shown in Figure 6(B). The turn on voltage in the case
which in turn would enable recombination’s
Delivered to occur
by Publishing at of ethanol
Technology was 4.5 University
to: McMaster V, which was lower than that of DI
a lower threshold voltage. ThisIP: event sequence resulted
117.253.107.242 On: Fri,water and2015
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12:52:32
in two observations first the turn-onCopyright:
voltage was lower Scientific
American Publishers
tion potential of ethanol which is 10.65 eV 20 that is lower
as compared to the other two analytes. This measurement
(A) Intensity of OLED with methanol
× 103
6
(A) Intensity of OLED with ethanol
Output voltage (mV)

5 × 103
____ OLED 5
Output voltage (mV)

4
____ Methanol 4 ____ OLED
3
3 ____ Ethanol
2 5V
2 4.5 V
1
1
0
0 1 2 3 4 5 6 7 8 9 0
–1 0 1 2 3 4 5 6 7 8 9
Input voltage (V) –1
Input voltage (V)

(B) Dynamic range of detection of methanol (B) Dynamic range of detection of ethanol
800
Output voltage (mV)

900
Output voltage (mV)

700
800
600 700
500 600
400 500
300 400
300
200
200
100 100
0 0
0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200
Concentration of methanol (ppm) Concentration of ethanol (ppm)

Fig. 5. (A) Graph showing the response of the OLED sensor to
methanol. The representation is for concentration of 800 ppm of
methanol. For the entire dynamic range the change in the output voltage
follow a similar trend post turn on voltage of 5 V, but the absolute values
of output voltages increased as the concentration of methanol increased.
(B) Linear dynamic range of detection of methanol using the OLED
chemical sensor. There was an increase in the output light intensity as
the concentration of methanol increased and this translated to an increase
in the output voltage from 30 mV to 700 mV.
Fig. 6. (A) Graph showing the response of the OLED sensor to ethanol.
The representation is for concentration of 800 ppm of ethanol. For the
entire dynamic range the change in the output voltage follow a similar
trend post turn on voltage of 4.5 V, but the absolute values of output
voltages increased as the concentration of ethanol increased. (B) Linear
dynamic range of detection of ethanol using the OLED chemical sensor.
There was an increase in the output light intensity as the concentration of
ethanol increased and this translated to an increase in the output voltage
from 50 mV to 800 mV.

6304 J. Nanosci. Nanotechnol. 9, 6299–6306, 2009

Devabhaktuni and Prasad Nanotextured Organic Light Emitting Diode Based Chemical Sensor

Table I. Summary of the threshold input turn-on voltage, the shift in the input threshold/turn-on voltage, the minimum output threshold output voltage
and the ionization potential of the specific analytes of the OLED chemical sensor under normal operating mode and during the chemical sensing mode.

Threshold input Shift in threshold Threshold output Ionization

voltage (V) input voltage (V) voltage (mV) potential

OLED 45 — 38 N/A

OLED with DI-water 525 075 184 12.58 eV
OLED with methanol 5 05 30 10.85 eV
OLED with ethanol 45 0 20 10.62 eV

was in line with the trend of decreased turn on voltage
(5.25 V, 5 V and 4.5 V respectively) with a decrease in
the ionization potential (12.58 eV, 10.85 eV and 10.65 eV
respectively) as observed among DI water, methanol and
ethanol.
may be possible to more specifically control the OLED
operating characteristics while functioning as a sensor.
We observe that the ionization potential for DI-water
is the highest; this suggests that it requires more energy
for it to ionize and release the electrons, which may be
the reason for the requirement of increased voltage to

3.4. Performance Metrics for Hydrocarbon Sensing
The dynamic range of detection for methanol was from
1000 ppm to 10 ppm and the dynamic range of detection
for ethanol is from 1000 ppm to 1 ppm. The limit of detec-
tion was identified as 10 ppm for methanol and 1 ppm for
ethanol. Limit of detection is defined as the lowest con-
centration that can be detected accurately by the chemical
sensor. The experimental parameter that was used to deter-
mine accuracy was the signal to noise ratio. If the detected
output electrical voltage was at least three times greater
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background noise.
American Scientific Publishers
There is a linear increase in output voltage with increase
in concentration for both the aliphatic hydrocarbon ana-
lytes, which suggests that the number of charge carriers
increase with an increase in concentration and thereby also
impacting the turn-on voltages.
The Table I below summarizes the threshold input volt-
ages (turn-on voltage), and output voltages (intensity of
OLED at turn-on voltage) of OLED with its cathode
coated with the different analytes of different ionization
potentials.
4. DISCUSSION
In this paper we have demonstrated the potential of using
an OLED for visual chemical detection of hydrocarbons
from aqueous solutions. We have demonstrated individ-
ual hydrocarbon detection for two aliphatic hydrocarbons
methanol and ethanol at 1 ppm and 10 ppm limit of detec-
tion respectively, by identifying specific turn-on voltages
and output intensities relevant to the chemicals. The varia-
tion in the turn-on voltages and output intensities with each
chemical is due to the difference in ionization potentials
required by the chemicals to release the valence electrons.
We also observe that the nanotexturing of the emissive and
conductive layer interface does contribute to the reduced
turn-on voltages, which is important while designing low
power sensors. Hence, by optimizing the nanotexturing it
RESEARCH ARTICLE
facilitate recombination between electrons and holes, thus
increasing the turn-on voltage. The two hydrocarbons have
a lower ionization potential as compared to DI water,
hence the turn on voltage for both the hydrocarbons was
observed to be lower than that of DI water. In addition
ethanol with a lower ionization potential as compared to
methanol demonstrated a lower turn-on voltage. The other
interesting aspect is that ethanol has the same turn-on
voltage as that obtained from the OLED when operating
under normal or non-chemical sensing mode; this sug-
gests that ethanol ionizes rapidly and much faster than the
chemicals, University
when introduced onto the OLED sensor
surface.
The OLED based detection technique despite being an
optical detection technique is still label-free. This has
been achieved by exploiting the organic nanotextured multi
stack OLED and perturbing the electron–hole recombina-
tion rate in the multi stack organic layers. The advantage
of using the nanotextured multi-stack OLED is that the
bias voltage is reduced and this is due to the mono charge
layers used for different charge carriers and the organic
layers being mono-transport i.e., they transport a single
type of charge ( either electrons or holes). The intensi-
ties of luminescence are in the range of visible spectrum
and the resulting color of the light is green. This spectrum
depends upon the active layer, which in the current appli-
cation is AlQ3 . Peak intensity occurs at 516 nm, which is
green in the visible spectrum.
Despite the advantage of developing an optical label-
free sensor there are multiple experimental process param-
eters that need to be optimized and controlled for proper
functioning of the device as a sensor. In order for OLED
to function properly the ITO layer (anode) thickness
needs to be controlled before depositing organic layers.
While depositing the organic layers while nanotexturing
is needed, there shouldn’t be any pinholes. The gaps in
the polymer layer during deposition are called pinholes
due to their size. These pinholes affect the functionality of
the OLED. The layers must be deposited keeping the stud
(mount to which the chip is attached) at a distance so that

J. Nanosci. Nanotechnol. 9, 6299–6306, 2009 6305

 Nanotextured Organic Light Emitting Diode Based Chemical Sensor
the other layers are not thermally perturbed resulting in
inactive layer depositions. By properly adjusting the thick-
ness of the layers and optimizing the nanotexturing the
OLED turn-on voltage can be reduced. The alignment of
the photo diode impacts the maximization of the absorp-
tion of the emitted light.
The advantage with these OLED’s is that they operate
both in pulsed mode and continuous mode power sup-
ply. However for the sensing application these devices are
operated in the continuous mode. In this mode, the energy
bands of these organic semiconductors (emissive and con-
ductive layers) are such that there is no temperature loss.
OLED-based sensors are robust, portable, cost effective
and fast. These types of sensors can find applicability
in applications such as mining, and in chemical factories
where there is a chemical spill for rapid, visual, label free
RESEARCH ARTICLE
indication of the trace presence of a toxic agent. This sen-
sor is called label free because it does not use any external
fluorescent tags or labels with the analyte that is tested but
utilizes the modulation to the electroluminescent capabil-
ity of the device as a function of the chemical analyte as
a mechanism for chemical sensing. The disadvantages of
the OLED sensor technology are their long term stability
and re-use. With an increase in recombination the width
of the junction barrier increases, therefore it becomes dif-
ficult for the charge carriers to break through the junction,
thereby reducing the operating time. Using
Delivered a multi-array
by Publishing Technologybyto:W.McMaster
cathode structure these OLED based chemical sensors can
IP: 117.253.107.242 On: Fri, 23pp.Oct 2015 12:52:32
be used for multi-chemical sensing. Copyright: American Scientific
5. CONCLUSION
We have demonstrated the design, fabrication and devel-
opment of a nanotextured OLED based chemical sen-
sor for rapid, visual, label free detection of aliphatic
hydrocarbons-methanol and ethanol. The detection mech-
anism is optoelectronic in nature where the impingement
of the chemical species on the cathode of the multi-
stack OLED modulates the electron–hole re-combination
physics resulting in a change in the emission characteris-
tics of the OLED namely its turn-on voltage and intensity
of emitted light. The device has been tested for individual
chemical detection. (With a deviation of 0.173 mV)
In the current prototype the device is capable of iden-
tifying the chemical up to the lower concentrations of
ppm (10 ppm for methanol and 1 ppm for ethanol) and
in addition the device is able to detect a single chem-
ical efficiently and we also we would like to improve
its detection for mix of chemicals by using arraying
6306
Devabhaktuni and Prasad
techniques. Optimizing the stack thickness an investigating
alternate emissive and conductive polymers can achieve
these. The future work is directed towards improving the
performance metrics of the device namely: decreasing the
limit of detection, improving selectivity. Finally the goal is
to implement the sensor for air based as well as aqueous
media based samples.
Acknowledgments: We would like to thank Dr. Carl
Wamser’s laboratory in the Department of Chemistry, Port-
land State University for providing the fabrication facilities
as well as useful discussions. We would also like to thank
Oregon Nanoscience and Micro technologies Institute for
partially funding this effort.
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Received: 15 September 2008. Accepted: 14 January 2009.
J. Nanosci. Nanotechnol. 9, 6299–6306, 2009