.

Synthetic Metals 111112 2000 133137

www.elsevier.comrlocatersynmet
Large area, full-color, digital image sensors made with semiconducting
polymers
Gang Yu
)
, Gordana Srdanov, Jian Wang, Hailiang Wang, Yong Cao, Alan J. Heeger
UNIAX, 6780 Cortona Drie, Santa Barbara, CA 93117-3022, USA
Abstract
The high performance polymer photovoltaic cells and photodiodes demonstrated recently are of great interests not only for traditional
applications but also for large area, digital image sensing. In this presentation, we demonstrate large sensing area, photodiode arrays and
matrices made with semiconducting polymers and polymer blends. These photosensors are of high photosensitivity, low dark current,
large dynamic range and fast response time. For full-color image sensing applications, large area photosensor arrays were developed to
. have true-color 24-bits resolution. The red, green, and blue color primaries were achieved by coupling a set of color filters with the
polymer sensor pixels with response to visible light radiation. Image recovery process from the pixel photocurrent data was developed,
which is suitable generally to image arrays with power law light intensity dependence and with finite pixel dark current. Large sensing
. . length photodiode arrays 2.55 in. were fabricated in 40100 dot-per-inch dpi . They were used as the sensing unit in page-size
document scanners. Voltage-switchable polymer photodetectors were developed. Their photosensitivity can be switched on and off with
external bias. These devices can be used as the sensing elements in xy addressable sensor matrices. The high onroff switching ratio and
high photocurrentrdarkcurrent ratio allow such two-dimensional, passive photosensor matrices to be used for image sensing applications.
q2000 Elsevier Science S.A. All rights reserved.
Keywords: Semiconducting polymers; Optoelectronic devices; Full-color image sensors
1. Introduction
Electroluminescent effect in organic semiconductors has
attracted broad attention among research scientists and
1

device engineers. This effect light emission due to

.
recombination of injected electrons and holes can be used
for fabricating emissive displays with process advantages
and with high luminous efficiencies. In addition to the use
for backlighting, large area segmental andror pixelated
displays have been demonstrated.
1

On the other hand, the invert process electric current

.
generation under light illumination in organic semicon-
w x
ductors can also be very efficient 1 . The photoresponse of
semiconducting polymers can be further enhanced by pho-
.
toinduced charge transfer CT , which separates electrons
)
Corresponding author. Fax: q1-805-562-9144.
. E-mail address: gangyu@uniax.com G. Yu .
1
Recent progresses were discussed extensively in this conference.
Many display prototypes were also demonstrated during the conference.
w x
and holes, and prevents early time recombination 212 .
The discovery of photoinduced CT in composites of con-
.
ducting polymers as donors, D and buckminsterfullerene,
.
C , and its derivatives as acceptors, A provided a
60
molecular approach to high efficiency solar cells and high
w x
sensitivity photodetectors 24 . Since the time scale for

photoinduced CT is subpicosecond faster than all compet-

.
ing processes , the quantum efficiency for charge separa-
tion between donor and acceptor is close to unity. Through
control of the morphology of the phase separation into an
interpenetrating bi-continuous network of D and A phases,
one can achieve high interfacial area within a bulk mate-
rial: a bulk DrA heterojunction material for efficient
charge separation. Moreover, the bicontinuous network
provides the needed pathways for collecting the separated
carriers at the external electrodes, holes from the donor
phase and electrons from the acceptor phase. Thus, thin
film sandwich devices with a bicontinuous DrA compos-
ite as the active material function as efficient photodetec-
w x
tors with high carrier collection efficiency 812 . High
performance photosensors in the metalrpolymerrmetal
0379-6779r00r$ - see front matter q 2000 Elsevier Science S.A. All rights reserved.
. PII: S0379- 6779 99 00327- 6
( ) G. Yu et al.rSynthetic Metals 111112 2000 133137 134
configuration have been demonstrated with external quan-
.
tum efficiency EQE close to or even beyond 100% elrph
w x
810 . These polymer photosensors can be fabricated by
simple coating or printing processes at low temperature.
Such processes allow the photosensors to be made in large
sizes, in flexible forms or onto curved substrates for
detecting light with complicated wavefronts.
In addition to traditional applications, the thin film
polymer photodetectors can be used as pixel elements of
w x
large area, image sensors 13 . These image sensors have
high photosensitivity, low dark current, large dynamic
range and fast response speed. Combining with a set of
optical filters, full-color image sensing in the visible spec-
tral range has been demonstrated. By proper selection of
the sensing materials andror optical filters, photosensors
in other spectral ranges such as in UV and near-infrared
can also be achieved.
2. Large size polymer photodiode arrays
For imaging applications in visible spectrum, the spec-
tral response of the sensor pixels should cover wavelengths
between 400 and 700 nm. This can be achieved with a

polymer blend containing regio-regular poly 3-alkyl thio-

. . w x
phene P3AT and 6,6 -PCBM. PCBM is a derivative of
w x
C with improved solubility 8 . Their molecular struc-
60
tures are shown in Fig. 1. Both P3AT and PCBM are
soluble at room temperature in common organic solvents
such as chloroform or 1,2-dichlorobenzene. The blend
solutions were prepared in the following procedure. First,
two master solutions of P3AT and PCBM were prepared
and stirred at room temperature. The blend solutions with
defined concentrations were then obtained by mixing the
two master solutions in proper molecular ratios. The blend
solution was then stirred at room temperature for 12 h
before film casting. The resulting blend solutions were
clean and uniform. The P3AT:PCBM blend films were
spin cast from the blend solution at room temperature.
High quality, uniform blend films can be achieved at spin
speed between 800 and 3000 rpm. No phase structures
. . Fig. 1. Molecular structures of P3AT donor and PCBM acceptor .
Fig. 2. Structure of the polymer photodiode arrays.
larger than 0.5 mm was observed. The resulting film

thickness is in the range of 10004000 A. Large area over
2
.
6=6 in dimension , high quality films have been demon-
strated with this process.
Photodiodes made in the configuration of ITOr
P3AT:PCBMrmetal show high photosensitivity, low dark
current and large dynamic range from mWrcm
2
down to
nWrcm
2
, similar to that shown in MEHPPV:C ,
60
w
MEHPPV:PCBM and MEHPPV:CNPPV blends 8
x
10 . The photosensitivity at 500 nm is typically 60180
mArW at 0 V bias, which corresponds to an EQE of
;20% elrph. The dark current near 0 V bias is ;0.11
nArcm
2
. The IV characteristics and optoelectric perfor-
w x
mance are similar to that in our early publication 12 . To
demonstrate the feasibility of large area image sensing,
linear photodiode arrays were fabricated containing 102
.
sensing elements in the format of 40 dot-per-inch 40 dpi .

The total sensing length of the array is thus 2.55 in 64.8

.
mm , longer than any Si photodiode arrays commercially
available. Photodiode arrays fabricated in other formats
.
include 1=480 arrays over 4.8-in sensing length 100 dpi
.
and 1=200 arrays over 5-in sensing length 40 dpi . The
device performance was insensitive to the device configu-
rations.
A cross-sectional view of the linear photodiode arrays is
shown in Fig. 2. In contrast to existing image sensing
technologies, a continuous photosensing layer is used in
this design. The pixel dimension is defined by the sizes of
the cathode and anode electrodes. This fabrication process
is quite similar to that used for polymer displays. The
polymer image sensing arrays can, thus, be fabricated with
the same manufacture lines used for polymer displays.
With such simple device structure and fabrication process,
large area image sensing arrays can be fabricated with
costs comparable to that for polymer displays. The pro-
jected cost per unit area is much lower than that for other
image sensing technologies.
3. Color identification
There are two common approaches in the construction
of red, green, and blue color pixels for image sensors. The
( ) G. Yu et al.rSynthetic Metals 111112 2000 133137 135
. Fig. 3. Spectral responses of P3HT:PCBM sensor pixel dotted line and
. . . red squares , green diamonds , and blue circles color pixels.
first is to combine three mono-color pixels made with
different sensing materials that exhibit spectral response to
three primary colors. The second is to use three sensor
pixels made with a wide-band sensing material with a
photoresponse covering the entire visible spectrum. In the
latter case, color recognition is achieved by combining the
three wide-band pixels with a set of color filters. Although
both approaches have been adopted in the display industry,
the second approach has been the favorite one for image
sensors due to its relatively simple fabrication process and
easy in achieving the spectral response necessary.
The color filter approach was adopted to construct the
color pixels of the polymer image sensors in this study.
P3HT:PCBM was used for the sensing materials of the
sensor pixels. As shown in Fig. 2, the onset of the photore-
sponse is at ;670 nm, with a small tail extending beyond
.
700 nm due to optical absorption in PCBM . In contrast to
that in photodiodes made with inorganic semiconductors,
the photoresponse of polymer photodiodes is relatively flat
w x
in visible spectral region 8 . The red, green, and blue color
pixels were achieved by placing the corresponding color
filter in front of the sensor array. Band-pass filters were
used for the blue and green pixels, and long-wavelength-
pass filters were used for the red pixels. The long wave-
length cut-off of the red pixels was determined by the
photoresponse of the sensing polymer blend. The photore-
sponses of the colored pixels are also shown in Fig. 3. The
data indicate that the color pixels of the polymer sensor
arrays are of high color purity.
.
The practice of color wavelength selection from a
wide-band sensor can be extended to multiple channels
beyond three. Coupling with a set of narrow-band optical
filters or with a narrow-band optical filter with variable
center wavelength, the polymer photodiode array can be
used for spectrographic applications. In addition to the use
for full-color image sensing, the P3HT:PCBM sensor ar-
rays can also be used as blackrwhite image sensors.
Moreover, due to its flat photoresponse in the 400600 nm
range, the P3HT:PCBM sensor can be used as optical
powermeter directly for radiometric applications. No addi-
tional compensation filter is needed.
[ ]
4. Digital imaging in 24-bit color format 14
Large area, two-dimensional image sensing was demon-
strated with a polymer scanner. It was constructed by
replacing the sensing and optical units of a commercial
scanner with a 1=102 photodiode array with a 0.635-mm
pitch size. The imaging process is similar to that of the
commercial document scanners. A color image was pro-
jected and focused on the surface of the color sensor array.
The image was read out by scanning the photodiode array
line-by-line in the longitudinal direction. The 40 dpi reso-
lution was guaranteed by setting the shift step equal to the
pixel size of the sensor array. The color information at
each position was decomposed into red, green and blue
color primaries by placing the red, green and blue filters in
sequence in front of the sensor array. The intensity of the
image at each color primary was detected by the photodi-
ode with the corresponding color filter. By this process,
the color image was collected through three scans, and was
transformed into three sets of analog photocurrent data
matrices. With three rows of polymer photodiode arrays
.
of which each row is arranged for one color primary , the
color image can be grabbed in single scan.
The photocurrent of the polymer sensor pixels follows a
power law relation with the incident light intensity. A
typical data set for P3HT:PCBM is shown in Fig. 4. The

power index is 0.97, close to unity i.e., linear intensity

.
dependence . This linear dependence allows the incident
light intensity to be represented directly by the photocur-
rent with negligible deformation. For a digital image with
an 8-bit dynamic range, the gray levels of the image can be
Fig. 4. Intensity dependence of polymer sensor pixels.
( ) G. Yu et al.rSynthetic Metals 111112 2000 133137 136
recovered by digitizing the recorded photocurrent data
matrices following Eq. 1:
n I PC
s s , 1 .
255 I PC
max max

where n is the digitized color value an integer between 0

.
to 255 for 8-bit resolution , I is the light intensity, I is
max
the maximum light intensity normalized to the highest gray
level 255, and PC and PC are the corresponding pho-
max
tocurrents. Eq. 1 can be generalized to image pixels with
nonlinear intensity dependence. For organic photodiodes,
power law intensity dependence is often observed: i.e.,
PC;I
a
, where a is an arbitrary number. For such a
power law, the light intensity can be restored from the
recorded photocurrent by the following expression:
1
a
I PC
s . 2 .
1
I
max
a
PC
max
The pixel dark current is sometimes the limiting factor
to the maximum gray levels. This dark current can also be
corrected before digitalization by the following equation:
1
a
r ,g ,b r ,g ,b
n I PC yDC .
s s , 3 .
1
255 I
max
a
r ,g ,b
PC yDC
.
max
where DC is the dark current value.
In practice, these restoration steps can be carried out
digitally after recording the image data into a computer.

Alternatively, the corrections dark current subtraction and

.
light intensity restoration can be carried out by corre-
sponding circuit unit in readout circuit prior to digitization.
The latter is a favorite from the process time point of view.
In the color image reproducing process, the maximum
photocurrents measured under the individual r, g, b filters
were digitized to 255, and the intensity information con-
tained in the photocurrent data matrices was converted into
8-bit digital data matrices. The dark current of each pixel
in the polymer photodiode array was typically three orders
of magnitude lower than the maximum photocurrent, which
means that no dark current correction was necessary. The
final image was recovered by overlaying the red, green,
and blue color images together. Since each color data set
was digitized to 8-bit gray levels, a true-color resolution
.
24-bit digital colors was achieved. This 24-bit color
format is also known as multi-million color format in
digital imaging field.
Fig. 5 shows two images recorded with a 1=102
polymer photodiode array and recovered following the
procedure described above. They were plotted in real sizes.
The width of the image is determined by the sensing
length of the polymer sensor array. No optical elements
Fig. 5. Digital color images in 24-bit color format scanned by the
polymer scanner. The real image sizes were 2.55
Y
=8.60
Y
and 2.55
Y
=
8.00
Y
.
were used to manipulate the image size. Residual graini-
ness in the spatial resolution arises from the 635-mm
.
pixel size 40 dpi . Photodiode arrays were also fabricated
over 5-in. sensing length in 40 and 100 dpi. Image sensing
experiments with 5-in. sensor arrays are still being carried
out, the results will be discussed in the near future.
5. Discussion
The gray levels of the polymer photodiode array are not
w x
limited to 256. As demonstrated earlier 810,12 , these
organic photodiodes response to the incident intensity lin-
early from mWrcm
2
down to nWrcm
2
, over six orders of
magnitude. This large dynamic range allows image digiti-

16
.
zation with high resolution. A gray level of 65 536 s2
can be achieved with 16-bit analog-to-digital converters.
The color combination with the color filter set is then 2
48

14
.
s2.8=10 . The polymer image sensors are thus of
great potential for high quality imaging applications.
( ) G. Yu et al.rSynthetic Metals 111112 2000 133137 137
Voltage-switchable polymer photodiodes were devel-
w x
oped in our laboratory recently 15 . The photosensitivity
can be switched on at a given bias, and switched off at
another. These devices can be used as the sensing elements
in xy addressable, two-dimensional sensor matrices. The
high onroff switching ratio and high photocurrentrdark-
current ratio allow such two-dimensional, photosensor ma-
trices be used for image sensing applications. With such
two-dimensional sensor matrices, large size color images
can be grabbed without moving parts.

Combining with a phosphor layer for energy up or

.
down conversion , a large area, polymer image sensor can
be used for image detection in other spectral ranges, such
w x
as infrared, deep UV, X-ray and high energy particles 15 .
The polymer-based image sensors offer significant pro-
cess advantages. As shown in Fig. 2, the polymer sensing
layer can be cast as a simple uniform film without pattern-

ing in contrast to the complex patterning processes in-

volved in fabricating the sensing layer in sensor arrays
.
made with inorganic semiconductor crystals . For the con-
jugated polymer-based sensor arrays, the fabrication pro-
cess is simplified even beyond that of passive liquid-crystal
displays. Moreover, the thin film polymer sensors can be
hybridized with other opticalrelectronic devices to form
integrated systems with smart functions. For example,
polymer sensor arrays can be used as image elements on
top of a CMOS driver array on a Si wafer to improve the
pixel filling factor to ;100%, or to form other types of
smart pixels. Image sensors fabricated on a curved surface
or on a flexible substrate provide unique opportunities to
detect complicated wavefronts, or to be used as curved
focal-plane image sensors. By bending a linear photodiode
array made onto ITOrmylar substrate into a semicircle,
the angular distribution from a point light source has been
w x
measured 16 . As shown in Fig. 3, the thin film organic
photodiodes are also sensitive to UV radiation. By means
w x
of a UV pass filter 12 , or by choosing an organic material
w x
with optical gap larger than 3.1 eV 17 , visible-blind UV
detectors have been demonstrated with organic semicon-
ductors.
6. Summary
In summary, large area, full-color image sensing was
demonstrated with organic photodiode arrays. These or-
ganic image sensors offer high photosensitivity, low dark
current, large dynamic range and fast response time. They
are fabricated with simple coating techniques at room
temperature, processes that can be implemented at a rela-
tively low cost. Photodetection with desired response pro-
.
file or multi-band full-color selection have been demon-
strated. By proper selection of the sensing materials andror
optical filters, photosensors suitable for detection in other
spectral ranges such as the near infrared and the UV can
also be achieved. These large area, organic sensors provide
alternative technology for image sensing applications. They
are also unique for many novel applications, which are
hardly achievable with traditional image sensing devices.
Acknowledgements

This work was partly supported by NSF SBIR Ph-I

.
DMI 9660975, SBIR Ph-II DMI 9801432 , and by ONR-
.
NAWC SBIR Ph-II N00421-97-C-1075 .
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