The most recent application of OLEDs: Structurally-integrated OLED-based luminescent chemical & biological sensors Ruth Shinar Microelectronics Research Center & ECpE Dept, ISU Integrated Sensor Technologies, Inc. (ISTI) Joseph Shinar All of the aforementioned & ISTI Support by DOE, NASA, NSF , & NIH also gratefully acknowledged
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The most recent application of OLEDs: Structurally-integrated OLED-based luminescent chemical & biological sensors Ruth Shinar Microelectronics Research.
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The most recent application of OLEDs:
Structurally-integrated OLED-based
luminescent chemical & biological sensors
Ruth Shinar
Microelectronics Research Center & ECpE Dept, ISU
Integrated Sensor Technologies, Inc. (ISTI)
Joseph Shinar
All of the aforementioned & ISTI
Support by DOE, NASA, NSF, & NIH also gratefully acknowledged
Sensing elementSensing element: : a porous film with an embedded luminescent dye, surface immobilizeda porous film with an embedded luminescent dye, surface immobilized
species, or microfluidic channels with recognition elements in solution species, or microfluidic channels with recognition elements in solution
PhotodetectorPhotodetector: : photomultiplier tube, Si photodiode photomultiplier tube, Si photodiode
Electronics and readoutElectronics and readout
Not IntegratedNot Integrated
Issues:Issues: Light-source is either bulky, or the integration with the sensing Light-source is either bulky, or the integration with the sensing
element/microfluidics involves intricate design (fibers, lens)element/microfluidics involves intricate design (fibers, lens) Sensors are often immobile, costlySensors are often immobile, costly Sensors are limited in use for real-world applications; often used for single Sensors are limited in use for real-world applications; often used for single
analyte detectionanalyte detection
Long-Term Goal:Long-Term Goal:
PD
long-pass filter
OLED
band- pass filter sensing component
glass
glass
a-(Si,Ge):H photodetector
OLED PD PD
Back-detection modeBack-detection mode
long-pass filter
glass
low gap a-(Si,Ge):H PD
transparent cover
OLED OLED OLED
band-pass filter over OLED pixels
OLED
microfluidic wells
Front-detection modeFront-detection mode
OLEDs Advantages for Sensor ApplicationsOLEDs Advantages for Sensor Applications
Are simple to fabricate and uniquely simple to integrate Are simple to fabricate and uniquely simple to integrate
with a sensing componentwith a sensing component Can be easily fabricated in any 2-D shapeCan be easily fabricated in any 2-D shape Are compatible with microfluidic structuresAre compatible with microfluidic structures Can be fabricated on plastic substratesCan be fabricated on plastic substrates Can be operated at an extremely high brightnessCan be operated at an extremely high brightness Consume little power and dissipate little heatConsume little power and dissipate little heat Cost is expected to drop to a near-disposable levelCost is expected to drop to a near-disposable level
ApproachApproach:structural integration of two structural integration of two componentscomponents:
OLEDs are easily fabricatedOLEDs are easily fabricatedas an array of pixelsas an array of pixels
Sensor operation modes:Sensor operation modes:
(1)(1) monitoring changes in monitoring changes in II
(2)(2) monitoring changes inmonitoring changes in
Back-detectionBack-detection
mode usingmode using
an array of an array of
OLED pixelsOLED pixels photodetectorphotodetector
glasssubstrate
ITOITO
OLEDOLED layerslayers
cathode
Luminescent sensor
OLEDOLEDpixelspixels
EL P LL PP LL
EL
liquid or gas analyteliquid or gas analyte
cathode
1. Oxygen Sensor 1. Oxygen Sensor
R. Shinar et al., Anal. Chim. Acta R. Shinar et al., Anal. Chim. Acta 568568, 190 (2006), 190 (2006)
Principle of operation:Principle of operation:
An oxygen sensitive dye is embedded in a thin film matrix or dissolved in solutionAn oxygen sensitive dye is embedded in a thin film matrix or dissolved in solution
Collisions of OCollisions of O22 with the dye result in quenching of the PL intensity with the dye result in quenching of the PL intensity II and shortening of and shortening of the PL decay time the PL decay time
II00 and and 00 – unquenched PL intensity and decay time; – unquenched PL intensity and decay time; KKSVSV - Stern-Volmer constant - Stern-Volmer constant
Sensor operation modes: (1) monitoring changes in Sensor operation modes: (1) monitoring changes in II (2) monitoring changes in (2) monitoring changes in
The need for optical filters and frequent calibrationThe need for optical filters and frequent calibrationis eliminated when using the PL decay time mode.is eliminated when using the PL decay time mode.
Results for Gas-Phase Oxygen:Results for Gas-Phase Oxygen:
Rubrene (0.5%)-dopedRubrene (0.5%)-doped AlqAlq33//Pd octaethylporphyrin Pd octaethylporphyrin ((PdOEPPdOEP) in a polystyrene film) in a polystyrene film
% O2
0 20 40 60 80 100
0/
0
50
100
150
200
250
Wavelength (nm)
350 400 450 500 550 600
Ab
sorb
ance
0.0
0.5
1.0
1.5
S S [[00//((100%100% OO22)]~240)]~240
PdOEPPdOEP
emission ~645 nmemission ~645 nm
Results for Dissolved Oxygen:Results for Dissolved Oxygen:
2. Recent Improvements in OLED-Based Oxygen Sensors: 2. Recent Improvements in OLED-Based Oxygen Sensors: Dispersion of TiO Dispersion of TiO22 Particles in the PS:PtOEP Film Particles in the PS:PtOEP Film
Enables use of reduced brightness for enhanced OLED lifetime and reduced Enables use of reduced brightness for enhanced OLED lifetime and reduced
photo-degradation photo-degradation [Zhou et al., Adv. Func. Mater. [Zhou et al., Adv. Func. Mater. 1717, 3530 (2007)], 3530 (2007)]
A uniquely simple approach, using 360 nm-diameter TiOA uniquely simple approach, using 360 nm-diameter TiO22 particles. particles.
Enhancement is due to light scattering by the high refractive index particles, & possibly by Enhancement is due to light scattering by the high refractive index particles, & possibly by voids induced by the particles.voids induced by the particles.
Typically, the sensor films were prepared by drop casting 40-60Typically, the sensor films were prepared by drop casting 40-60 LL of the solution of the solution onto the glass substrate; the resulting films were all ~ 8onto the glass substrate; the resulting films were all ~ 8 mm thickthick
SEM images of PS films doped with PtOEP and titania particles: SEM images of PS films doped with PtOEP and titania particles: (a)(a) 2 mg/mL TiO2 mg/mL TiO22 in the solution used for film fabrication, (b) 8 mg/mL particles in the solution used for film fabrication, (b) 8 mg/mL particles..
(a) (b)
The PL spectra in air, excited at ~The PL spectra in air, excited at ~535535 nm by the nm by the AlqAlq33 OLEDOLED, of , of PtOEPPtOEP:PS doped with :PS doped with
different concentrations of TiOdifferent concentrations of TiO22, measured in reflection geometry., measured in reflection geometry.
In Air
The effect of titania particles on the PtOEP:PS The effect of titania particles on the PtOEP:PS PLPL decay curves and on the decay curves and on the ELEL of the of the AlqAlq33 OLEDOLED in a 100% gas-phase Ar environment at 295 K. Shown is the intensity measured by in a 100% gas-phase Ar environment at 295 K. Shown is the intensity measured by the PD during and following the 50the PD during and following the 50 ss AlqAlq33 OLED OLED pulse at titania particle concentrations pulse at titania particle concentrations of 0, 1.5, 2, 4, and 8 mg/mL. A 610 nm long-pass filter was placed in front of the PD, so of 0, 1.5, 2, 4, and 8 mg/mL. A 610 nm long-pass filter was placed in front of the PD, so that only a small fraction of the OLED emission reached the PD. Inset: the PL signal that only a small fraction of the OLED emission reached the PD. Inset: the PL signal enhancement vs. the titania particle concentration. enhancement vs. the titania particle concentration.
Gas-Phase
The PL decay curves in Ar- and OThe PL decay curves in Ar- and O22-saturated solutions for: (a) PtOEP and (b) PdOEP with -saturated solutions for: (a) PtOEP and (b) PdOEP with
and and
without titania doping; the exponential (Ar) and bi-exponential (Owithout titania doping; the exponential (Ar) and bi-exponential (O22) fitting are also shown.) fitting are also shown.
(a)
DO in Water
Green Alq3 OLED/PtOEP
The green The green AlqAlq33 OLED array is behind the OLED array is behind the PtOEPPtOEP-film, which is largely confined to a -film, which is largely confined to a
region in front of the middle two OLED pixels.region in front of the middle two OLED pixels.
The The greengreen emission from these pixels combines with the emission from these pixels combines with the redred PL of the PL of the PtOEPPtOEP dye to dye to
produce the observed produce the observed yellowishyellowish spots. spots.
The photodetector is located behind the OLED array.The photodetector is located behind the OLED array.
Example of sensor design & operation – Example of sensor design & operation – GreenGreen OLEDOLED//PtOEPPtOEP embedded in polystyrene embedded in polystyrene
R. Shinar et al., SPIE Conf. Proc. 6007, 600710-1 (2005).
Multianalyte Sensor in Operation: consecutive sensing using a Multianalyte Sensor in Operation: consecutive sensing using a single photodetectorsingle photodetector
small-size sensor array (e.g., total size small-size sensor array (e.g., total size ~1.5x1.5 cm~1.5x1.5 cm22))
sensing element: Osensing element: O22-sensitive dye (-sensitive dye (PtOEPPtOEP) ) and an analyte-specific oxidase enzymeand an analyte-specific oxidase enzyme
each sensing element is associated with 2 each sensing element is associated with 2 OLED pixelsOLED pixels
sensing of the different analytes in a single sensing of the different analytes in a single sample is obtained by addressing the sample is obtained by addressing the appropriate OLED pixelsappropriate OLED pixels
simultaneous sensing of the different analytes simultaneous sensing of the different analytes in a single sample is obtained when all OLED in a single sample is obtained when all OLED pixels are lit simultaneously, and the PL of pixels are lit simultaneously, and the PL of each analyte is monitored by its associated Si each analyte is monitored by its associated Si photodiode. A Labview program enables such photodiode. A Labview program enables such simultaneous monitoring via separate simultaneous monitoring via separate channels.channels.
ITO anode
OLED pixel
Al cathode
silicon photodiode array
6 mm
Y. Cai et al., Sensors & Actuators B 134, 727 (2008).
In reactions performed in In reactions performed in sealedsealed wells, where there is no replenishing of O wells, where there is no replenishing of O22, and , and
the initial concentration of the analyte does not exceed that of the initial DO the initial concentration of the analyte does not exceed that of the initial DO
(~0.25 mM in water at 23(~0.25 mM in water at 23ooC)C)::
Sensing in Sealed Wells: Assessing the limit of detectionSensing in Sealed Wells: Assessing the limit of detection
Peptides with donor and acceptor on either side of the cleaving site are synthesized
In this D-A configuration, the fluorescence of the donor is quenched by the acceptor
Following exposure to LF, the peptide is cleaved; the donor and acceptor are
separated, resulting in an increase in the detected intensity of the donor fluorescence.
cleaving site
Selected examples showing the effect of the concentration of the peptide on the photoluminescence using 25 nM LF
Time (min)
0 10 20 30 40 50 60
PL
Ch
ange
(%
)
0
10
20
30
40
50
60
70
3.2 M
4.5 M
7.5 M
22.5 M
37.5 M76.5 M The maximal increase in the PL
following exposure of the labeled peptide to LF was by a factor of 2 at 37 oC
To improve sensitivity, need to eliminate OLED tail that overlaps the donor emission.Turn to Ru dye (exc=385 nm, red emission):bis(2,2’-bipyridine)-4’-methyl-4-carboxybipyridine-Ru N succinimidyl ester-bis(hexafluorophosphate)& QSY21 quencher.
5. Hydrazine (N2H4)
Highly toxic but popular NASA monopropellant & common precursor in the
synthesis of some polymers, plasticizers and pesticides M. P. 2°C, B. P. 113.5°C, room temp vapor pressure 14.4 torr Gov’t recommended exposure limit is 10 ppb for 8 hrs Immediately dangerous to life or health at ~50 ppm Detection based on reaction of hydrazine with
anthracene 2,3-dicarboxaldehyde (ADA).
Reaction product emits at 549 nm (exc= 476 nm) Signal proportional to N2H4 concentration Good for air, solution Fast and very selective response
S. Rose-Pehrsson and G. E. Collins, US Patent 5,719,061)
ADA
H
H
PL change upon ADA exposure to 60 ppb hydrazine in Ar
Envisioned fully integrated OLED/sensing film/thin film PD array in a back Envisioned fully integrated OLED/sensing film/thin film PD array in a back
detection configuration. Grounded Al stripes between the OLEDs and PDs will detection configuration. Grounded Al stripes between the OLEDs and PDs will
block the edge EL and the synchronous electromagnetic noise generated by block the edge EL and the synchronous electromagnetic noise generated by
modulated OLEDs.modulated OLEDs.
long-pass filterlong-pass filter
glassglass
glass/PDMSglass/PDMS
low gap a-(Si,Ge):H PDlow gap a-(Si,Ge):H PD
wells or wells or microfluidic microfluidic channels channels
transparent covertransparent cover
Towards complete integration: front detectionTowards complete integration: front detection
OLEDOLED OLEDOLED OLEDOLED
Band-pass filter over OLED pixelsBand-pass filter over OLED pixels
Second Step: single element; front detectionSecond Step: single element; front detection
structural integration of three components:structural integration of three components:
OLEDOLED//sensingsensing elementelement//PD; PD; II mode of operation mode of operation
The three-component integration is attractive due to the potential for The three-component integration is attractive due to the potential for
miniaturization of sensor arrays, their fabrication on flexible substrates, and miniaturization of sensor arrays, their fabrication on flexible substrates, and
integration with microfluidicsintegration with microfluidics
R. Shinar et al., J. Non Cryst. Solids R. Shinar et al., J. Non Cryst. Solids 352352, 1995 (2006)., 1995 (2006).
OLED lightOLED light
gas flow
530 nm band-pass filter
long-pass filter
sensor
PD
PDsPDs
PECVD-grown p-i-n and n-i-p structures, based on a-Si and a-(Si,Ge), or PECVD-grown p-i-n and n-i-p structures, based on a-Si and a-(Si,Ge), or
nc-Si.nc-Si.
The p-i-n structures were fabricated on an ITO-coated glass substrate; the The p-i-n structures were fabricated on an ITO-coated glass substrate; the
ITO was protected from reduction by the hydrogen plasma with a 0.1 ITO was protected from reduction by the hydrogen plasma with a 0.1 m m
thick ZnO layer grown by RF sputtering.thick ZnO layer grown by RF sputtering.
The composition and thickness of the p & i layers were tuned to increase The composition and thickness of the p & i layers were tuned to increase
the sensitivity at wavelengths matching the emission band of the oxygen-the sensitivity at wavelengths matching the emission band of the oxygen-
sensitive dye and to reduce the sensitivity to the OLED background.sensitive dye and to reduce the sensitivity to the OLED background.
The emphasis was on The emphasis was on
(a)(a)improving the Oimproving the O22 detection sensitivity by improving the PDs & reducing detection sensitivity by improving the PDs & reducing
the synchronous OLED-generated electromagnetic noise the synchronous OLED-generated electromagnetic noise
(b)(b)understanding factors that affect the speed of the PDsunderstanding factors that affect the speed of the PDs
The PDs were first tuned for high sensitivity at the PtOEP/PdOEP emission wavelength The PDs were first tuned for high sensitivity at the PtOEP/PdOEP emission wavelength
(~635/650 nm) and minimal response at the OLED excitation (~535 nm). The a-(Si,Ge)-(~635/650 nm) and minimal response at the OLED excitation (~535 nm). The a-(Si,Ge)-
based PDs are preferred due to their match with the dye PL, and lower response at the EL based PDs are preferred due to their match with the dye PL, and lower response at the EL
band. However, their dark current was higher and their speed lower.band. However, their dark current was higher and their speed lower.
TUNING of the PDsTUNING of the PDs
Wavelength (nm)500 600 700 800
Qua
ntum
Eff
icie
ncy
0.0
0.1
0.2
0.3
0.4
0.5
a-Si:Ha-Si:H a-(Si,Ge):Ha-(Si,Ge):H (0.7 m)
Wavelength (nm)
350 400 450 500 550 600A
bso
rban
ce0.0
0.5
1.0
1.5
2.0
2.5
emission ~635emission ~635 nmnm
PtOEPPtOEP (0.5 m)0.15 m p-layer
0.3 m p-layer1.6% Ge in p-layer10% Ge in i-layer
Detection of the photoluminescence of PtOEP embedded in polystyrene by the a-(Si,Ge):H- based photodetector, using a 600 nm long-pass filter
Detection of the photoluminescence ofDetection of the photoluminescence of PtOEP PtOEP embedded in polystyreneembedded in polystyreneby the a-(Si,Ge):H- based photodetector using a 620 nm band-pass filterby the a-(Si,Ge):H- based photodetector using a 620 nm band-pass filter to to reduce the background, and therefore increase the sensitivity.reduce the background, and therefore increase the sensitivity.
Single elementSingle element: front detection: front detection
Initial integration resulted in low Initial integration resulted in low S S attributed to a large attributed to a large background stemmingbackground stemming from the broad OLED EL, and high PDs’ dark current.from the broad OLED EL, and high PDs’ dark current. A major reason to the low A major reason to the low SS is the synchronous electromagnetic is the synchronous electromagnetic (EM) noise from (EM) noise from the pulsed OLED when using lockin detection of the intensity.the pulsed OLED when using lockin detection of the intensity. SS improved significantly by improved significantly by shielding the OLED. shielding the OLED.
To shield the PD from this EM noise, a grounded 150 nm thick ITO-coated To shield the PD from this EM noise, a grounded 150 nm thick ITO-coated
glass was placed above the OLED.glass was placed above the OLED.
Towards operation in the Towards operation in the modemode
Concluding Remarks
OLED science and technology is undergoing explosive growth Structurally integrated OLED-based sensors are very promising Organic photovoltaics & organic field-effect transistors are also
growing at an extremely rapid clip. They deserve a separate
treatment. See Sumit Chaudhary’s ECpE course on Organic