JOURNAL OF DISPLAY TECHNOLOGY, VOL. 6, NO.

3, MARCH 2010 87

Display Technology Letters

Inkjet Printed RGB Quantum Dot-Hybrid LED
Hanna M. Haverinen, Risto A. Myllylä, and Ghassan E. Jabbour, Member, IEEE

Abstract—We report DC driven full color inkjet printed color photoluminescence emission from inkjet printed QDs
quantum-dots light-emitting devices. The inkjet was used to excited via an AC driven inorganic phosphor layer [6], and
print monochromatic red, green, and blue, as well as integrate
red–green–blue light-emitting quantum dots unto a substrate single color inkjet printed QDLED [7], there has been, to the
having QVGA display. The performance of the inkjet printed best of our knowledge, no report published on DC driven RGB
monochrome devices was on the same order as that of spin QDLED array that has been fabricated via inkjet printing.
coated ones. For the full color RGB devices, a video brightness of
100cd m2 is achieved at 9.3 V. In this paper, we present first demonstration of QVGA pat-
Index Terms—Inkjet printing, quantum dot (QD), QVGA RGB
terned RGB QDLED where each R, G, and B colored QDs solu-
QDLED. tion is deposited via inkjet printing of picoliter volumes directly
onto the substrate. We will also highlight the effects of pinholes
and energy transfer on the printed QDs device performance.
I. INTRODUCTION
UANTUM-DOT light-emitting devices (QDLEDs) have II. DEVICE FABRICATION
Q raised interest in display research due to their excep-
tional color purity, stability, and high quantum yield.
We first proceed to demonstrate printing of pixilated R, G,
and B QDLEDs, each on their respective substrate, followed by
Potentially QDLED can reach OLED luminous efficiency yet integrated RGB on the same substrate. All devices have QVGA
capable to be more power efficient [1]. Furthermore, these pixel count. Due to common electrode configuration, fabrication
quantum sized lumophores are liquid processable thus making of monochrome QDLEDs was necessary in order to characterize
quantum dots attractive from processing point of view by and assess the operation of individual colors (R, G, and B) prior
enabling low cost full color display manufacturing. Despite to their integration in full color format.
the rapid progress in QDLED research, it has been difficult The quantum dots used in this study are based on CdSe core,
to demonstrate direct RGB pattering that is suitable for an ZnS passivating shell, and an organic monolayer used to en-
industrial process. In this regard, deposition of QDs for light hance the solution forming ability of the QDs when dissolved in
emitting applications has been limited to spin coating [2], mist a given solvent. In this study, all quantum dot solutions had the
coating [3], and stamp printing [4]. Among these techniques, same concentration of 2.5 mg/ml, where a 1:1 ratio of toluene:
only stamp printing can yield efficient multi-color pixelated dichlorobenzene was used as a solvent. The red dots (size 5.0
QDLEDs. However, each color requires a two-step deposition nm) emit at nm 10 nm wavelength, green dots (size 3.4
process: 1) spin coating of QDs onto stamp, and 2) transfer nm) emit at 540 nm 10 nm and blue dots (size 3.2 nm) emit
of QDs layer to the substrate. With spin coating included in at nm 10 nm, respectively.
such approach, the materials loss is still high (ca. 94%–97%). The solutions were loaded into three 10 pico-liter cartridges
This along with the potential difficulty arising from alignment of a Fuji Film Dimatix Materials 2830 series printer. Each car-
accuracy needed for stamping the various color pixels on an tridge had 16 piezo driven nozzles which can be addressed sep-
industrial scale renders this approach too expensive to adopt arately and arranged horizontally at a pitch of 254 m. In this
in its present form. Inkjet printing, on the other hand, offers work, only one nozzle was used at a time. The red and green
both simplicity of deposition in predefined pattern and much ink droplets had the same spacing, whereas blue ink had signifi-
reduced materials cost due to the drop-on-demand option which cantly smaller drop spacing. Determination of each drop spacing
deposits QDs in minute quantities and in predefined places on and piezo driver wavefunction was based on a study reported
the substrates to within an order of micrometer registration previously by the authors [7].
accuracy [5]. Although there has been a demonstration of full The ITO (20 sq ) substrates were cleaned ultrasonically,
followed by the deposition of photoresist, and its patterning
Manuscript received October 23, 2009. Current version published February and curing using standard photolithographic methods to yield a
10, 2010. The work of H .M. Haverinen was supported by TEKES (Finnish
Funding Agency for Technology and Innovation), Graduate School of Modern QVGA (640 480) pixel geometry. No etching of the ITO was
Optics and Photonics. performed. Each photoresist pixel had an L-shape with an area
H. M. Haverinen and Prof. R. A. Myllylä are with the Optoelectronics and of 19600 m and spacing between adjacent pixels of 80 m.
Measurement Techniques Laboratory, University of Oulu, 90014 Oulu, Finland.
G. E. Jabbour is with the School of Materials, Arizona State University, The substrates were then exposed to a 2 min oxygen plasma
Tempe, AZ 85287 USA, and also with Optoelectronics and Measurement treatment in order to remove organic contaminants and increase
Techniques Laboratory, University of Oulu, 90014 Oulu, Finland (e-mail: the ITO workfunction. Hole injection layer poly[3,4-ethylene-
jabbour@asu.edu).
Color versions of one or more of the figures in this paper are available online
dioxythiophene] doped with poly[styrenesulfonate] (PEDOT:
at http://ieeexplore.ieee.org. PSS) was then spin coated at 5000 rpm for 60 s and post-baked
Digital Object Identifier 10.1109/JDT.2009.2039019 for 30 min at 150 in air, resulting film thickness of 30 nm.
1551-319X/$26.00 © 2010 IEEE

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88 JOURNAL OF DISPLAY TECHNOLOGY, VOL. 6, NO. 3, MARCH 2010

Fig. 2. QDLED emission showing EL originating mostly from QDs. R and B

spectra were taken at 15 V, and that of G QDLEDs at 20 V.
Fig. 1. General device structure for all QDLEDs made for this study.

The substrates were then moved into a nitrogen filled glove

box where they were re-heated to 120 for 5 min to rid the
surface of water moisture that might have been absorbed during
transport. A hole transport layer (HTL) of photocross-linkable
poly-TPD [poly-(N,N-bis(4-butylphenyl-N,N-bis(phenyl)ben-
zidine)] was then spin coated on top of the PEDOT:PSS. The
HTL was prepared by dissolving 6 mg of the polymer in chlo-
roform. A spin speed of 2000 rpm for 60 s was used. Following
the polymer deposition step, UV-curing was carried at 245 nm
for 10 min to ensure complete cross-linking. The polymer HTL
thickness was measured to be 40 nm. The substrates were then
removed into air where the QDs printing step was carried.
Fig. 3. Brightness versus. bias voltage for R, G, and B devices having printed
For monochromatic devices, the entire substrate (1 in 1 in) QDs layer.
was printed with QD ink, while for RGB each color was printed
according to the sequence RGBRGBRGB… Since the printer the small peak around 410 nm in the B QDs EL spectrum repre-
system allows only one monochrome cartridge to be used at a sent a combination of p-TPD (peak at ca. 400 nm) and TPBi
time, the printing of the three QDs solutions required changing (peak at ca. 380 nm) emission, thus indicating incomplete ex-
the cartridges and maintaining an accurate registration of citon transfer from the organic layers to the B QDs. The broader
each printing step to avoid color contamination. Following emission seen between 380 nm–500 nm for the G and R QDs
the printing step, devices were heated at 180 C for 10 min is characteristics of exciplex formation between poly-TPD and
in nitrogen environment to remove absorbed water and the TPBi, which is due to possible pinholes in the printed layers
capping organic ligand [8]. giving rise to direct contact between molecules of the two or-
A 40-nm layer of thermally evaporated small molecules of ganic materials. The origin of these pinholes could be due to
TPBi 1,3,5-tris(2-N-phenylbenzimidazolyl)benzene was uti- non-jetting row and/or misalignment of jet stream resulting from
lized as electron transport layer, followed by the deposition of a printer vibration.
cathode consisting of 1.5 nm of LiF and 140 nm Al [9], [10]. In All devices operated at relatively low bias between 4–5 V
order to assess better the performance of devices having inkjet indicating a very thin QD layer (on the order of a monolayer) [6].
printed QDs layer, reference devices using the more established The overall performance of red devices was the best, followed
spin coating of QDs solutions were also fabricated and tested. by green and blue devices, respectively. A maximum brightness
of 352 cd m (EQE ca. 0.23%) was measured at 17.5 V for
III. RESULTS red device, Fig. 3. Green devices reached peak brightness of
270 cd m (EQE 0.15%) at about 18 V, where as blue devices
A. Monochromatic Devices had the lowest peak brightness of 122 cd m (EQE ca. 0.1%)
In Fig. 2, electroluminescence (EL) spectra of each R, G, and at 16.5 V. It is worth noting that the performance of devices
B QDLED is shown. having inkjet printed layers was on the same order of magnitude
Spectra were taken at 15 V for R and B devices, and at 20 as those using a spin coated QDs layers in agreement with our
V for G devices. Measured R emission peak is at 605 nm, G previous findings [7]. Fig. 4 shows a photograph of about 232
at 550 nm, and B at 475 nm. Using CIE (Commission interna- pixels of each color operating in EL mode. All pixels are under
tionale de l’éclairage) color coordinates and measured spectra common cathode and anode having a device area of 0.14 cm .
shown in Fig. 2, the calculated color coordinates corresponding Exciplex formation and incomplete energy transfer con-
to R, G, and B are (0.57, 0.37), (0.34, 0.56) and (0.12, 0.13), tribute negatively to the quantum efficiency of QDLEDs.
respectively. The figure shows strong electroluminescence with Nonradiative complete energy transfer from the organic mate-
light predominantly emanating from the QDs with slight con- rials to the QDs was demonstrated to be the major contributor
tamination originating from the organic layers. In this regard, to EL of QDLEDs [4]. In addition to the nonradiative energy

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HAVERINEN et al.: INKJET PRINTED RGB QUANTUM DOT-HYBRID LED 89

Fig. 4. High magnification photographs of printed devices under operation re-

vealing their pixel-array geometry.

Fig. 6. Luminance of RGB devices vs. bias voltage. A peak brightness of 350
cd=m is recorded at 17.5 V.

IV. CONCLUSION
We were able to demonstrate the feasibility of inkjet printing
approach to deposit QDs in predefined pixel pattern having a
QVGA format. The successful operation of the RGB printed
devices indicates the viability of inkjet printing approach in
the fabrication of full color QDLEDs for display application.
However, further optimization of print quality is still needed in
order to eliminate pinholes formation, thus maximizing energy
Fig. 5. RGB spectrum measured at 10 V. Insert: photograph showing strong transfer from organic layers to the QDs and in turn increasing
emission from red pixels which overshadow the emission from remaining G the performance of the devices.
and B pixels. The overall device area is 0.14 cm with both ITO, and metal as
common electrodes to all array elements. ACKNOWLEDGMENT
One of the authors, H .M. Haverinen, thanks Dr. X. Yang and
transfer, the EL, and in turn the efficiency, of QDLEDs can R. Sliz for technical support. One of the authors, G.E. Jabbour,
be affected to lesser extent by direct formation of the exci- thanks the Academy of Finland, Distinguished Professor of Fin-
tons on the QDs through electron and hole injection from land program, and F. Dimatix for their support. The authors also
surrounding organic layers (e.g., thank S. Ageno of the Flexible Display Center for providing the
and ; and patterned substrates.
[6], where is the highest
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