Influence of thickness and position of an ultrathin yellow layer on color
tuning (including white) of Organic Light Emitting Diodes
H. Choukri1, A. Fischer1, S. Forget1, S. Chénais1
T. Billeton1, M-C. Castex1, D. Adès2, A. Siove2
Institut Galilée (1LPL, 2LBPS, CNRS), Université Paris 13
93430 Villetaneuse
FRANCE
choukri@lpl.univ-paris13.fr
siove@galilee.univ-paris13.fr
Abstract – Non-doped white organic light-emitting diodes using
(i) a yellow-emitting ultrathin layer of rubrene (5,6,11,12-
tetraphenylnaphtacene) inserted on the either side of the
interface of a hole-transporting α-NPB (4,4’-bis[N-(1-naphtyl)-
N-phenylamino]biphenyl) layer and a blue-emitting DPVBi
(4,4’-bis(2,2’-diphenylvinyl)-1,1’-biphenyl) layer, (ii) a hole-
injecting layer of CuPc (copper pthalocyanine), (iii) an electron-
transporting layer of Al(Q)3 (aluminium tris[8-
hydroxyquinolinate]), are described. Both the thickness and the
position of the rubrene layer within the hole transporting layer
of α-NPB and the blue-emitting film of DPVBi allow to achieve
the desired color from deep blue with CIE coordinates (x= 0.17,
y= 0.15) and an external quantum efficiency ηext= 3.4%, (at
30mA/cm2), to pure yellow with CIE (0.51, 0.48) and ηext=1.3%,
via a bright white (WOLED) with excellent CIE coordinates (x=
0.33, y= 0.32), a ηext of 1.9%, a color rendering index (CRI) of 70
and a luminance of 2230cd/m² at 60mA/cm². Such a single-well-
like structure provides a fine tuning of the emission color by
means of the adjustment of the exciton diffusion zone via the
« exciton-confinement » layer of rubrene.
Index Terms—White Organic Ligth-Emitting Diode,
color-tuning.
I. INTRODUCTION
Organic light emitting devices (OLEDs) are a promising
technology for fabrication of full-color flat-panel displays.
The successful development of OLEDs relies on the
capability to obtain emission spanning the full visible
spectrum. In particular, White OLEDs (WOLEDs) are of
foremost interest for lighting and display applications [1].
To achieve white emission from electroluminescence
devices based on organic dyes, various methods have been
used such as e.g. multilayer diodes using the combination of
the three primary colors Red, Green and Blue (RGB) or two
complementary color emission (as blue and orange or
yellow) in a doped-type structure [2-4], multiple-quantum-
well architecture [5], exciplex formation [6]. Among these
various devices, numerous doped-type WOLEDs using two
emission colors to produce white have been fabricated
[3,4,7,8]. In these devices, although the co-evaporation
process allows, to a certain extent, a control of the emitted
radiation color via the different evaporation rates of the blue
and yellow emitters, it remains technologically difficult to
attain an accurate control of the dopant concentration. Hence,
fine tuning of the quality of the white emission is still
problematic. Non-doped-type WOLEDs using blue and
orange emitters [9] or blue and yellow [10] have been
recently reported. In the latter case a sub-monolayer of 0.1
1-4244-0136-4/06/$20.00 '2006 IEEE 4865
N. Lemaitre, C. Denis, P. Maisse, B. Geffroy
Laboratoire Composants et Cellules CEA-Saclay/LITEN
91191 Gif sur Yvette Cedex
FRANCE
bernard.geffroy@cea.fr
nm of rubrene was inserted at the NPB/DVPBi interface
and color emission was changing by varying the relative
thickness of DVPBi or Al(Q)3. Although white emission
was obtained, fine tuning of the light between blue-
yellow-white remains difficult as the yellow emitter
deposit cannot be changed neither in thickness nor in
position within the recombination zone. Moreover, the
control of the quantity of rubrene at the interface, as well
as the understanding of the physical processes, is not
facilitated by the small thickness of the so-called “layer”
(about ten times thinner than a molecular monolayer).
Herein, we report on a way to achieve balanced white
emission in a multilayer OLED based on blue matrices
of α-NPB and DVPBi 50 and 60 nm thick respectively,
in which we inserted a tunable ultrathin yellow emitter
layer of rubrene. We show that by adjusting both the
thickness and position on either side of the α-
NPB/DVPBi interface, a very accurate control of the
emitted color can be obtained. Starting from deep blue
with CIE coordinates (x=0.17, y= 0.15) and ηext= 3.4%,
(at 30mA/cm2) the color can be shifted to pure yellow
with CIE (x=0.51, y=0.48) and ηext=1.3%, via a bright
white with excellent CIE coordinates (x= 0.33, y= 0.32)
close to the equi-energy white point (x=0.33,y=0.33),
ηext=1.9% and a quite good Color Rendering Index (CRI)
of 70. The external quantum efficiencies, chromaticity
coordinates and luminance values are investigated for
various thicknesses and positions of rubrene layer
sandwiched into the α-NPB and DVPBi films. It was
shown that to obtain a white with a good quality, rubrene
must have an optimum thickness of 1-2 nm (between a
mono- and a bilayer) and must be inserted within blue
films at a distance of, at most, 5 nm from the α-
NPB/DVPBi interface.
II. EXPERIMENTAL
A. Chemicals
Molecular structures of the different organic compounds
used in OLED fabrication are represented on fig. 1.
Aluminium tris(8-hydroxyquinolinate), Al(Q)3 (H.W.
Sands); copper pthalocyanine, CuPc (Aldrich); 4,4’-
bis[N-(1-naphtyl)-N-phenylamino]biphenyl, α-NPB
(H.W. Sands); 4,4’-bis(2,2’-diphenylvinyl)-1,1’-
biphenyl), DPVBi (H.W. Sands); 5,6,11,12-
tetraphenylnaphtacene, rubrene (Aldrich).

N
O
O
Al
N
N
O
Rubrene
N N
N Cu N
N N
CuPc
N N
α-NPB
DVPBi
Fig. 1. Chemical structure of the compounds used for OLEDs fabrication.
B. Devices fabrication and characterization
The 0.3 cm2-active-surface OLED-structure consists of
the different layers described in fig. 2. The Indium Tin-
Oxyde (ITO)-covered glass substrate was purchase from
Asahi. Its sheet resistance is about 15 Ω/sq. The ITO glass
plate was cleaned by sonication in a detergent solution and
then in deionized water. Organic compounds are deposited
onto the ITO anode by sublimation under high vacuum (10-7
Torr) at a rate of 0.2 – 0.3 nm/s. An in-situ quartz crystal was
used to monitor the thickness of the vacuum depositions. We
sequentially deposited onto the ITO anode a thin (10 nm)
layer of CuPc (copper phtalocyanine) as a hole-injecting
layer, then a 50 nm thick α-NPB layer as a hole-transporting
layer. A 60 nm thick DVPBi layer is then deposited and acts
as a blue emitter matrix. Finally, a thin (10 nm) Al(Q)3 layer
was used as electron-transporting layer onto the LiF/Al
(a)
Al(Q)3
(b)
Fig. 2. (a): structure of the devices when the Rubrene layer is in the
NPB (thicknesses are given in the text). (b): schematic energy level
diagram (in eV) when the Rubrene layer is in the DPVBi matrix.
top cathode.
An ultrathin layer of Rubrene was inserted within the
structure, at a position d from the NPB/DVPBi interface.
The position d of this layer was translated between -10
and + 20 nm i.e. either within the α-NPB layer (d =
-10nm) or within the DVPBi layer (d = +20nm) as
represented in fig. 2. (a). The thickness e of the Rubrene
layer was varied from 1 nm to 10 nm. All the
measurements were performed at room temperature and
under ambient atmosphere, without any encapsulation.
Electroluminescence spectra and chromaticity
coordinates were recorded with a PR 650 SpectraScan
spectrophotometer at a constant current density of
30mA/cm2. Besides luminous efficiency and chromatic
coordinates, another important quality of white light
emitters for illumination purpose is the Color Rendering
Index (CRI). The CRI defines how well colors are
rendered by different illumination conditions in
comparaison to a standard (i.e. a thermal radiator or
daylight). As defined by the Commission Internationale
de l’Eclairage [11], a set of eight calibrated samples with
different absorption spectra and a reference illuminant
are used to define the CRI. The adaptative color shift of
the human eye is also taken into account for the
calculation. The CRI is normalized so that a CRI of 100
would represent that all of 8 color samples illuminated
by the white light source in question, would appear to
have the same color as those same samples illuminated
by the reference source. The exact determination of the
CRI depends strongly on the choice of the illuminant,
which is not given in the CIE definition. The reference
source used for the CRI calculation is not given in the
CIE definition. To choose the appropriate illuminant, we
first calculate the Correlated Color Temperature (CCT)
(according to ref [12]) of our White OLED. The
reference source used for the CRI calculation is then the
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 TABLE I
Effect of the thickness and position of the rubrene layer on performances: turn-on voltage (V), external quantum efficiency ηext (%),power efficiency
(lm/W), current efficiency (cd/A), luminance (cd/m²), and CIE coordinates (x,y) of the devices. The lines in bold font represent White OLED.

Devices Rubrene Position d(nm) Performances CIE (x,y)

thickness e (nm) UT (V) ηext (%) (lm/W) (cd/A) (cd/m²) @30mA/cm²
NPB DPVBi @60mA/cm²
A 1 -1 _ 6.1 1.2 1.1 4.4 1584 (0.515, 0.480)
B 1 -3 _ 6.5 1.4 0.9 4.1 1689 (0.388, 0.377)
C 1 -3.5 _ 6.0 1.7 1.1 4.1 1795 (0.316, 0.305)
D 1 -5 _ 6.5 1.7 0.9 3.5 1700 (0.237, 0.272)
E 1 -10 _ 5.3 3.4 1.2 4.4 2275 (0.172, 0.147)
F 1 _ 0 5.9 1.2 1.2 4.6 1600 (0.510, 0.485)
G 1 _ +5 5.0 2.6 2.5 8.2 4067 (0.410, 0.432)
H 1 _ +10 6.0 2.0 1.0 3.7 1700 (0.246, 0.230)
I 1 _ +20 5.3 2.8 1.1 3.6 1900 (0.174, 0.151)
G 1 _ +5 5.0 2.6 2.5 8.2 4067 (0.410, 0.432)
J 2 _ +5 5.7 1.9 1.3 4.4 2234 (0.331, 0.322)
K 5 _ +5 6.6 0.6 0.4 1.5 708 (0.312, 0.292)
L 10 _ +5 6.8 0.5 0.3 1.1 566 (0.319, 0.298)

black body at this temperature if the CCT is less than 5500K,
and the D65 Daylight illuminant otherwise.
III. RESULTS AND DISCUSSION
The energy level diagram summarizing the Highest
Occupied Molecular Orbital (HOMO) and Lowest
Unoccupied Molecular Orbital (LUMO) levels (in eV) of the
different materials used in our structures is schematically
presented in fig. 2 (b).
The NPB/DPVBi interface appears as a barrier for holes
coming from the ITO anode (∆Ε= 0.5 eV between HOMO
levels) as well as for electrons coming from the Al cathode
(∆Ε= 0.4 eV between the LUMO levels). Excitons are then
expected to recombine mostly around this interface and
efficient blue-light emitting diodes of a similar structure
(doped and non-doped) have been reported [9,13-15].
As it has been shown that hole mobility in NPB is two
order of magnitude higher than the electron mobility in
Al(Q)3, itself being around three times higher than that in
DVPBi the performances of these blue OLEDs mainly
depend on the DVPBi thickness [13,16]. To take into account
the microcavity effects, we first optimized the DPVBi total
thickness (60 nm) using ETFOS software (Emissive Thin
Film Optics Simulator) [17] so that the recombination zone
was located at an antinode of the standing wave in the
microcavity (for the peak wavelength of DPVBi λmax= 456
nm). In order to investigate the color-control potential and
the performance of our structure, we varied both the rubrene
thickness (e) and the position of an ultrathin rubrene layer (d)
on either side of the NPB/DPVBi interface. Since the mean
value diameter of the rubrene molecule has been estimated at
around 1nm [16] we do not use thickness lower than this
value in order to work with, at least, a monolayer of the
yellow emitter.
Influence of (d) and (e) on performances and the CIE
coordinates for several devices are shown on Tab.I. The turn-
on voltage UT is given for 0.1 lm/W. All efficiencies –
external quantum efficiency ηext(%), power efficiency
(lm/W) and current efficiency (cd/A)- are given at 30mA/cm²
current density.
From the results mentionned in Tab.I, it appears that,
in terms of ηext, the optimum thickness of the rubrene
layer is e= 1-2 nm. For higher value of e, the
performances of the OLED decrease. When the position
d of a 1nm width of rubrene layer varies from 0 to 20 nm
around the NPB/DVPBI emissive interface, we control
the color emission from blue to yellow via white, while
keeping the efficiency relatively high.
Typical, blue, yellow and white emission spectra are
shown on fig.3. In these configurations, the emission
spectrum consists in two well balanced blue and yellow
peaks leading to a bright white emission control with
thicknesses of a “yellow well” corresponding to a mono
or bilayer of the rubrene molecule. This level of control
cannot be achieved with the classical co-evaporation
process where the yellow emitter is included, more or
less homogeneously, in the whole blue layer. The CRI of
the white devices have been estimated to around 70. On
the basis of the energy level diagram on the Fig. 2 b),
when the rubrene layer is far away from the NPB/DPVBi
interface, the emitted spectrum (see Fig. 3, Device E) is
dominated by the DPVBi emission, leading to a deep
blue OLED with CIE coordinates (x= 0.17, y= 0.15)
corresponding to the DVPBi emission light, and a
maximum efficiency of ηext= 3.4% for d = -10nm
(yellow-emitter in NPB). The corresponding luminance
is 2275cd/m² at 60mA/cm².
Pure yellow emission with CIE coordinates (0.51,
0.48) and ηext=1.3%, is achieved (see Fig. 3, Device A)
when the rubrene lies at the interface (d = -1nm) where
the emission occurs. These coordinates correspond to
those of the emission light of rubrene molecules [3].
White emission with excellent CIE coordinates (x=
0.33, y= 0.32), very close to the equi-energy white point
(0.33, 0.33), and ηext=1.9% was obtained (see Fig. 3,
Device J) for a thickness of e=2 nm and a position d =
+5 nm. The luminance is 2230cd/m² at 60mA/cm², and
13V applied voltage. White emission with CIE
coordinates of (0.32, 0.30) and ηext=1.7% is also

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Fig. 3. Typical blue (Device E), yellow (Device A) and white (Device C)
emission spectra at 30mA/cm² ( e= 1nm of rubrene in the NPB layer; d= -10
nm for (Device E), d= -1 for (Device A), d=-3.5nm for (Device C)).
Fig. 4. Evolution in the 1931 CIE chromaticity diagram of the (x,y)
coordinates of the emitted light with the rubrene layer position d at
30mA/cm² (the d value is figured near each data point) for a rubrene layer
thickness e = 1 nm. The negative values (black dots) concern the case of
rubrene in NPB layer.
obtained when a 1nm thick rubrene layer is positionned in
the NPB, 3.5 nm away from the NPB/DPVBi interface (d =
-3.5nm, Device C). The luminance is 1800cd/m² at
60mA/cm², and 13V applied voltage.
The CIE coordinates (x,y) for different positions of 1nm
rubrene ultrathin layer are plotted in Fig. 4. It is clear that we
can continuously adjust the emitted color of the device from
deep blue to pure yellow, along the line joining the CIE
coordinates of the DPVBi emission (x= 0.17, y= 0.15) and
those of the rubrene emission (x=0.51, y=0.48), by simply
moving the rubrene layer position. Hence, it can be drawn
that all the intermediate emission spectra arise from the
combination of that of the rubrene layer and that of pure
DVPBi layer. In our devices, it appears that after the
occurrence of the recombination process within narrow zone
around the NPB/DVPBi interface, a slice of exciton diffuses
in both direction towards anode and cathode and so is able to
attain the rubrene well whether it is not too far away.
Thus, emission is controlled by the diffusion of excitons
and their lifetime within the crossed layer i.e. NPB or
DVPBi. We could use our measurement to estimate roughly
the exciton diffusion length in both NPB and DPVBI.
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Fig. 5. Relative Rubrene intensity Ir for different positions in NPB and
DPVBi blue emitter hosts. The dots show the experimental datas, and
the line the exponential decay fitting.
The diffusion length LD is determined from Fig. 5 using
the exponential relation below between the position d in
the host and the relative emission intensity of Rubrene Ir
[17,18]:
− d
L
I r ∝ k ⋅ e D
where I r = I Rubrene ( I host + I Rubrene ) , IRubrene
and Ihost are the peak spectral intensities of yellow-
emitter Rubrene and host material NPB or DPVBI. This
is shown in Fig. 5 for the two hosts. k is a constant, LD
the diffusion length and d the position in the host (NPB
or DPVBI). The diffusion length LD of the excitons has
been estimated with this method to 4.9 ±1nm in NPB and
8.7 ±0.6 nm in DPVBI matrix. As the diffusion length LD
of excitons is higher in the DPVBi host than that of
NPB, blue emission may come in a mean part from
DPVBi and some from NPB.
The external quantum efficiency ηext (%) versus
current density for the best WOLED (Device J) are given
in Fig. 6 . At low current densities, the efficiency rises to
a maximum of 2.2% at about 5mA/cm², and then
decreases slowly for higher current densities. Between 1
and 50 mA/cm², the efficiency remains at about 2%,
which is due to the high PL quantum yield of Rubrene
[19]. The external quantum efficiency ηext (%) with
increasing Rubrene thickness is also given in Fig. 7. As
mentionned earlier, we observe that the performance of
the OLED decreases when the yellow-emitter Rubrene
thickness varies from 1 to 10 nm. Indeed, when the
Rubrene thickness is high, the electrons coming from the
LiF-Al cathode could be trapped in the Rubrene layer
due to the high difference of LUMO between DPVBi
and Rubrene (∆LUMO=0.4eV). As it was shown before
in Fig. 2. b), the interface NPB/DPVBi acts as a hole-
barrier (∆HOMO = 0.5eV), so there is no recombination
in Rubrene layer. This trapping effect is not effective for
thickness (e < 2nm) Rubrene layer as the electrons can
then pass through the well by tunnel effect.
 10 3,5

External quantum efficiency

External quantum efficiency n(%) 3
Device J @30mA/cm²
2,5

ηext (%)
2

1,5
1
1

0,5

0
0 1 2 3 4 5 6 7 8 9 10 11

0.1 Rubrene thickness e (nm)

0.1 1 10
Current density (mA/cm²)
Fig. 6. External quantum efficiency ηext (%) versus current density for
WOLED (2nm of Rubrene in DPVBi d=5nm).
IV. CONCLUSION
In summary, we showed that by adjusting both the
thickness and position of an ultrathin layer of rubrene on
either side of the α-NPB/DVPBi interface, a very accurate
control of the emitted color can be obtained. Starting from
deep blue with CIE coordinates (x= 0.17, y= 0.15) and ηext=
3.4%, (at 10mA/cm2) to pure yellow with CIE (0.51, 0.48)
and ηext=1.3%, via a bright white with excellent CIE
coordinates (x= 0.33; y= 0.32), ηext=1.9%, a quite good
Color Rendering Index (CRI) of 70 and a good luminance of
2230 cd/m² at 60mA/cm² were demonstrated. A solution to
open the door towards more complex structures is to use 3 or
more different emitters at various wavelengths, with
adjustable positions and thicknesses. Such a configuration
may improve OLED color control and particularly the CRI
value.
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