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Color Sensors with Three Vertically Stacked Organic Photodetectors

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2007 Jpn. J. Appl. Phys. 46 L1240

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Japanese Journal of Applied Physics
Vol. 46, No. 49, 2007, pp. L1240–L1242
#2007 The Japan Society of Applied Physics

Color Sensors with Three Vertically Stacked Organic Photodetectors

Hokuto SEO
, Satoshi A IHARA, Toshihisa W ATABE, Hiroshi O HTAKE, Misao KUBOTA, and Norifumi EGAMI
NHK Science and Technical Research Laboratories, Setagaya, Tokyo 157-8510, Japan
(Received September 20, 2007; accepted November 16, 2007; published online December 14, 2007)

A stacked structure composed of three organic photodetectors that were individually sensitive to only one of the primary color
components was fabricated based on tetra(4-methoxyphenyl) porphine cobalt complex, NN0 -dimethylquinacridone, or zinc
phthalocyanine, as blue, green, or red sensitive photoconductive materials, respectively. The spectral photoresponse char-
acteristics were measured, and the output signal from each detector showed good spectral selectivity, clearly demonstrating
color separation in the vertically stacked structure. Comparisons of the output signal currents of single structures (without
stacking) and the stacked structure revealed that 70% of the incident light reached the bottom layer of the stack.
[DOI: 10.1143/JJAP.46.L1240]
KEYWORDS: organic photodetector, photoconductivity, stacked color sensor, color separation

The photoconductive properties of organic materials have

ITO electrode
attracted much interest from both the practical and physical
points of view. For example, organic photoconductors are NTCDA layer
commercially used in copying machines. Furthermore, a Alq3 layer
photocurrent multiplication phenomenon of up to 10,000 Photoconductive layer

times has been observed, and this has been ascribed to an

ITO
interaction between the organic layer and the Au electrode.1) Glass substrate
An efficient high-speed photodetector that has a multilayer
structure composed of donor-acceptor alternating layers has
Incident light
been also demonstrated,2) and recently, a transparent organic Red Green Blue
photodiode for polarized light detection using an aligned
organic molecule layer was reported.3) Blue-sensitive Organic film
Our group has proposed a new type of image sensor photodetector for blue
overlaid with three organic photoconductive films that are Green-sensitive Organic film
individually sensitive to only one of the primary color photodetector for green

components (blue, green, or red light), with the aim of
developing a compact, high-resolution color camera without
the color separation optical systems used in current color
cameras.4) To attain high picture quality, broadcast tele-
vision (TV) cameras are equipped with a dichroic prism
and three image sensors [such as charge-coupled devices
(CCDs)]. Consumer video cameras and digital still cameras,
in contrast, have an optical color filter array pasted over a
single image sensor such as CCD or complementary metal–
oxide–semiconductor (CMOS) sensor to obtain compact
camera size, even though its inferior optical system degrades
spatial resolution and light use-efficiency to one third or less
of those of the dichroic prism system. As with photographic
film, color separation in the depth direction of the image
sensor could eliminate the necessity of the dicroic prism,
and could lead to a compact, lightweight single chip color
camera with high enough resolution and sensitivity for
broadcasting use. The stacked organic image sensor describ-
ed here leads us to realizing such a camera.
Our previous experiments confirmed that organic photo-
conductive films had excellent selectivities with respect to
a single primary color.4) The high-resolution characteristics
of organic films sufficient for high-definition TV were
also demonstrated using pickup tubes.5,6) In addition, a clear
output signal voltage from CMOS image sensors overlaid
with an organic photoconductive film was observed.7,8)
Takada et al. demonstrated monochromatic images from a
CMOS image sensor with a green-sensitive organic photo-


E-mail address: seo.h-js@nhk.or.jp
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Red-sensitive Organic film
for red
photodetector
Glass substrate
Fig. 1. Schematic diagram of stack structure and cross sectional view of a
photodetector.
conductive layer.9) The previous studies on organic photo-
conductive films suited for image sensor applications have
not dealt with stacked structures or their color separation
properties. However, there have been several reports on
stacked structures in the field of organic functional devices.
Uchida et al. demonstrated a stacked full-color pixel
composed of organic light emitting devices toward high-
resolution displays.10) Tandem structures11–13) and multiple
device stacked structures14) for organic solar cells have been
studied as a mean to increase power conversion efficiency.
In this study, we demonstrate color separation in a stacked
structure composed of three organic photodetectors that are
individually sensitive to blue, green, or red light. The output
signal from each detector showed good spectral selectivity
in accordance with our design, which could provide us an
application to stacked organic image sensors.
We fabricated three organic photodetectors composed of
blue-, green-, and red-sensitive organic photoconductive
films on individual glass substrates, and stacked these detec-
tors. Figure 1 represents the schematic configuration and the
cross-sectional view of a photodetector. When white light is
irradiated on the top of the stack, the blue component is
Jpn. J. Appl. Phys., Vol. 46, No. 49 (2007) H. S EO et al.

Table I. Structures and thicknesses of the fabricated device components. 3

(a)
Color Photodetector structures and thicknesses of the components 2
Glass(0.7 mm)/ITO(150 nm)/Co-TPP(80 nm)/Alq3 (220 nm)/ 1
Blue
NTCDA(400 nm)/ITO(20 nm)
0
Glass(0.7 mm)/ITO(150 nm)/NN0 -QA(200 nm)/Alq3 (50 nm)/ 0.4 (b)

Absorbance
Green
NTCDA(300 nm)/ITO(20 nm)
Glass(0.7 mm)/ITO(150 nm)/ZnPc(250 nm)/Alq3 (50 nm)/ 0.2
Red
NTCDA(300 nm)/ITO(20 nm)
0
2 (c)

1
absorbed in the top layer and the generated carriers are read
out from the indium–tin-oxide (ITO) transparent electrodes 0
400 500 600 700
of that layer. The green and red components of the incident Wavelength (nm)
light go through the layer. The green component is then
absorbed in the middle layer, and the generated carriers Fig. 2. Optical absorption spectra of the devices. Dashed line, solid line,
are read out from ITO electrodes of that layer. Finally, the and dashed-dotted line represent the blue-, green-, and red-sensitive
photodetectors, respectively.
red component is absorbed in the bottom layer, and the
generated carriers are read out from ITO electrodes of that
layer. If the wavelength selectivities of each photocon-
0.03
ductive film are ideal, the photodetectors can be stacked in
any order.
We chose tetra(4-methoxyphenyl) porphine cobalt com-
plex (Co-TPP), NN0 -dimethylquinacridone (NN0 -QA), and 0.02

zinc phthalocyanine (ZnPc) as blue, green, and red sensitive
photoconductive materials, respectively. The photodetector
structures are summarized in Table I. The films were
fabricated as follows. A photoconductive material (ZnPc,
NN0 -QA, or Co-TPP) was evaporated on a commercial glass
substrate coated with ITO electrode. Tris-8-hydroxyquino-
line aluminum (Alq3 ) and naphthalene tetra carboxylic
anhydride (NTCDA) were then consequently evaporated.
Finally, ITO film for the counter transparent electrode
was formed on the organic film by using DC magnetron
sputtering. DC power was 0.1 kW, and deposition rate was
2.5 nm/min. Since all the photoconductive materials have
hole transport properties, an Alq3 layer with an electron
transport property was incorporated in their films in order
to improve quantum efficiency. An NTCDA layer, inserted
between the Alq3 and sputtered ITO layer, acted as a buffer
layer15) to prevent electrical shorting caused by depositing
the ITO electrode on the organic layers.
Figure 2 shows the optical absorption spectra for each
photodetector. The blue photodetector showed absorption
peaks at 425 and 540 nm, which correspond to the absorp-
tions of the Soret-band and Q-band in Co-TPP, respectively.
The rapid increase in absorption intensity at less than 425 nm
is attributed to absorption in the thick Alq3 layer. The green
photodetector had absorption peaks at 500 and 540 nm.
Although this photodetector also absorbed in the blue
region, it transmitted red light longer than 600 nm. The
red photodetector had absorption peaks at 615 and 700 nm.
Absorption in the purple region shorter than 450 nm was
high in this photodetector, and this characteristic is attrib-
uted to absorption in the Alq3 layer.
Figure 3 summarizes the spectral photoresponse charac-
teristics of the stacked structure shown in Fig. 1. Mono-
chromatic light of 50 mW/cm2 was irradiated on the blue-
sensitive device side. The applied electric fields of blue,
green, and red sensitive films were 1:0  106 , 1:3  105 , and
1:6  105 V/cm, respectively. Positive bias was applied to
L1241
Sensitivity (A/W)
0.01
0
400 500 600 700
Wavelength (nm)
Fig. 3. Spectral photoresponse characteristics of stack structures. Dashed
line, solid line, and dashed-dotted line represent the blue-, green-, and
red-sensitive photodetectors, respectively.
the sputtered-ITO electrodes of all devices. The spectral
photoresponse curves of blue, green and red sensitive films
had respective peak wavelengths at 420 nm [full width at
half maximum (FWHM) of 40 nm], 510 nm (FWHM of
100 nm), and around 650 nm (FWHM of 240 nm). These
results clearly indicate that color separation occurred in the
vertically stacked structure of organic photodetctors. The
applied electric field to blue sensitive film was an order of
magnitude larger than those to green and red sensitive films,
which is mainly due to the widest energy gap of Co-TPP
among three photoconductive materials. Furthermore, thick
Alq3 layer (220 nm) in blue sensitive film compared with
those in other two films (50 nm) would also increase applied
electric field. Optimization for the thickness of Alq3 layer
in blue sensitive film could decrease applied electric field
closer to other two films.
The quantum efficiency, defined as the number of output
electrons divided by the number of irradiated photons, of the
blue-, green-, and red-sensitive films at their photocurrent
peak wavelengths were 0.08, 0.06, and 0.05, respectively,
which were not sufficient for the application to image sen-
sors. Thick organic layers are thought to limit the efficien-
cies because of the short diffusion length (5 to 100 nm)2)
of photo-generated excitons. The sputtering conditions for
Jpn. J. Appl. Phys., Vol. 46, No. 49 (2007)
0.04 (a)
0.03
Sensitivity (A/W) 0.02
0.01
0 resulted good color separation characteristics as shown in
0.04 (b)
0.03
0.02
0.01
0 thicknesses of the glass substrate and ITO electrodes and the
400 500 600
Wavelength (nm)
Fig. 4. Comparison of output signal currents of single structure (dashed
line) and stack structure (solid line) for (a) green and (b) red devices.
depositing the ITO electrodes need to be improved to
decrease the organic film thicknesses to 100 nm or less,
which could in turn increase the quantum efficiencies of the
films. Dissociation of electron-hole pairs generated by
photons at the interface between a donor (lower ionization
potential) and an acceptor (higher electron affinity) material
is well known to occur, which have been frequently used in
organic solar cells to increase their efficiencies. In this study,
Alq3 , which has no absorption in wavelength region longer
than 450 nm, was chosen as the acceptor-like material.
Though we had obtained the quantum efficiencies of 0.2 in
the layer structures of Co-TPP/Alq3 6) and ZnPc/Alq3 4) in
previous studies, a several-fold improvement in efficiency is
required. In addition to the optimization of film thicknesses,
therefore, the use of acceptor-like materials that has higher
electron acceptability with no absorption in visible wave-
length region, instead of Alq3 , would lead to increase the
quantum efficiencies.
Figure 4(a) compares the output signal currents for the
green photodetector of the single structure (without stacking)
and the stacked structure. The single structure had an
undesired output signal in the blue region, whereas the
stacked structure had a much smaller blue signal because
the top layer acted as a blue cut filter to the middle layer.
Moreover, the blue component absorbed in the top layer
became the blue signal, which could improve light-use
efficiency compared with that of the optical color filter array
system of conventional single-chip color cameras: light
absorbed in color filters is not converted into output signals.
In the stacked structure, about 70% of the output signal
compared with that in the single one was obtained at the
irradiated wavelength of 510 nm. In contrast, the output
signal decreased to 50% at 540 nm in the stacked structure,
due to the large absorption in the top layer (blue photo-
detector) as shown in Fig. 2(a).
The output signal of the red photodetector in the
stacked structure was about 70% compared with that in the
single structure for a wavelength range longer than 600 nm
[Fig. 4(b)]. This indicates that 70% of the red component in
the incident light reached the bottom layer. In addition, the
stacked structure decreased the output signal for blue and
green.
H. S EO et al.
The individual films in this study did not have excellent
color separation characteristics equivalent to the prisms and
optical color filters used in current color cameras, especially
in the shorter wavelength regions. However, stacking films
in the order of blue, green, and red from top to bottom
Fig. 3. Having films with better color separation character-
istics would eliminate the limitation on the stacking order of
the films, which is underway. The ratios of output signals in
the stacked structure to those of single structures should be
also increased, which could be improved by optimizing the
700
transmittance of the organic layers.
Photoresponse properties of the organic films are one of
the important factors to apply image sensors. We confirmed
that the red sensitive film has a frequency response > 2 kHz
by impulse response measurement using red laser diode,
which is sufficient for TV use (field frequency of typical TV
system is 60 Hz). Both the rise time of turn-on current and
the decay time of turn-off current are shorter than 1/60 s,
which means that the signals accumulated through a field
have not affected the next field in moving images.
In conclusion, we fabricated stacked structure of three
organic photodetectors that are individually sensitive to
only blue, green, or red light. The output signal from each
detector showed good spectral selectivity, clearly demon-
strating color separation in the vertically stacked structure.
To obtain a color picture image, a solid-state circuit that
reads out signals generated in each stacked organic film will
be necessary. Combining readout circuits with organic films
could move us a step closer to the realization of a compact
high-resolution color camera.
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