Synthetic Metals 127 (2002) 165±168

Blue light emitting diodes with bathocuproine layer

D. Troadeca, G. Veriotb, A. Molitona,*
a
UMOP, EA 1072, Faculty of Sciences, University of Limoges, 123 av. Albert Thomas, 87060 Limoges Cedex, France
b
LCR-THALES, Domaine de Corbeville, 91404 Orsay Cedex, France

Abstract

Several hole transport molecules (N,N0 -diphenyl-N,N0 -(3-methylphenyl)-1,10 -biphenyl-4,40 -diamine; 4,4-bis[N-(1-naphthyl)-N-phenyla-
mino]biphenyl; 4,40 ,400 -tris[N-(1-naphthyl)-N-phenylamino]triphenylamine (TNATA); MTDATA) are blue light emitters [SPIE 3797 (1999)
120]. Realisation of monolayer structures is very easy but their performances are too weak. To improve them, we have built some multilayer
structures with electron transport layer (tris(8-hydroxyquinolinate) aluminium (Alq3); bis(10-hydroxybenzo(h)quinolinate) beryllium
(Bebq2)) and a bathocuproine (BCP) layer to con®ne the radiative recombinations in the hole transport layer. To improve hole injection,
we inserted poly(3,4-ethylenedioxythiophene) (PEDOT) layer between the indium±tin-oxide anode and the hole transporting layer. The best
results are obtained with the four-layer structure PEDOT/TNATA/BCP/Bebq2 …l ˆ 508 nm†, luminance ˆ 5500 cd/m2 at 10.2 V.
# 2002 Elsevier Science B.V. All rights reserved.

Keywords: Hole blocking layer; Bathocuproine (BCP); Blue light emitting diode

1. Introduction 2. Experimental

Flat panel displays have been capturing the attention of Some of the used organic materials are synthesised at
the electronics industry for several years. Liquid crystal THALES LCR:
displays and new displays such as plasma, plasma assisted
 tris(8-hydroxyquinolinate) aluminium (Alq3),
liquid crystal and ®eld emission displays are now commer-
 bis(10-hydroxybenzo(h)quinolinate) beryllium (Bebq2).
cially available. On the other hand, in recent years, organic
The others are commercial:
electroluminescent materials and their applications to
 N,N0 -diphenyl-N,N0 -(3-methylphenyl)-1,10 -biphenyl-
organic light emitting diodes (OLEDs) have become increa-
4,40 -diamine (TPD),
singly important because of their potentials for low cost
 4,40 ,400 -tris[N-(1-naphthyl)-N-phenylamino]triphenyla-
manufacturing, mechanical ¯exibility, wide viewing angle,
mine (TNATA),
and high brightness. Furthermore, these materials have low
 4,4-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB),
operating voltages and a wide range of emission wave-
 2,9-dimethyl-4,7-diphenyl-1,10-phenantroline (bathocu-
lengths which allows one to realise full-colour and self-
proine: BCP),
luminous ¯at panel displays [1,2].
 poly(3,4-ethylenedioxythiophene)-PSS (PEDOT-PSS).
For green light, tris(8-hydroxyquinolinate) aluminium
(Alq3) is widely used as electron-transporting green-emissive The indium±tin-oxide (ITO) anode is deposited on a
material [3]. Considerable research has been undertaken 1.1 mm thick glass substrate. The ITO is commercially
for developing red OLEDs using ¯uorescent dopants such prepared by Merck Display Technologies and has a sheet
as DCM, coumarin [4], Nile Red [5], perylene or europium resistance of about 20 O/sq. that corresponds to typically
complexes [6]. For blue emissions, zinc complexes or 100 nm thick ®lm. Prior to the organic deposition, the ITO
¯uorene-oxadiazole compounds [7] are reported as elec- coated glass plate is cleaned in an ultrasonic bath.
tron-transporting blue emitting materials. But their perfor- The conducting polymer (PEDOT-PSS) and its solvent are
mances are weak and they show poor colour purity. ®ltered (0.45 mm) and deposited by spin coating; the ®nal
In this paper, we studied blue light emission of the hole thickness is 40 nm. The TPD, NPB, TNATA, BCP, Bebq2
transporting layer in monolayer and multilayer structures. and Alq3 are prepared in a vacuum chamber (about
*
Corresponding author. Tel.: ‡33-5-55-45-74-32;
10 6 Torr) by vapour deposition from heated molybdenum
fax: ‡33-5-55-45-72-88.
Ê /s and the distance
boats. Typically, the deposition rate is 2 A
E-mail address: [email protected] (A. Moliton). substrate-boat is about 12 cm. Generally, the thickness of the

0379-6779/02/$ ± see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 9 - 6 7 7 9 ( 0 1 ) 0 0 6 1 5 - 4
166 D. Troadec et al. / Synthetic Metals 127 (2002) 165±168

hole transport layer (HTL) is around 60 nm, and for each best results are obtained with the structure ITO/PEDOT-
studied structure we will specify the thickness of each layer. PSS/TNATA/Ca/Al with luminance 240 cd/m2 and thresh-
After the organic layer sublimations, the sample is trans- old voltage 3.3 V.
ferred into a vacuum chamber (10 5 Torr) inside a glove Tang and VanSlyke [9] inserted an HTL before the EL
box. The cathode, about 150 nm of calcium covered with (Alq3) which is an electron transport layer (ETL) to improve
150 nm of aluminium is then deposited on top of the organic the hole transport. In our case, the EL is an HTL, and so we
layers using two different tungsten evaporation boats. The insert an ETL between EL and the cathode to improve the
active area of the emissive layer (EL) device, de®ned by the electron injection.
overlap of the ITO anode and the Ca/Al cathode, is However, experiment showed ETL electroluminescence
7.11 mm2. instead of HTL electroluminescence, as we could forecast on
The EL luminance is measured with a photodiode and a energy diagram (Figs. 1 and 2a).
Keithley 175 multimeter, the intensity with a Keithley 617 To solve this problem, we inserted a BCP layer between
electrometer and the EL spectrum with a Zeiss spectro- ETL and HTL. On the one hand, the high barrier in the
photometer. All the measurements are realised at room HOMO levels located between HTL and BCP (0.7 eV)
temperature and under nitrogen controlled atmosphere. allows us to block the holes in the HTL; on the other hand,
the low barrier in the lowest unoccupied molecular orbital
(LUMO) levels between BCP and HTL (0.1 eV) facilitates
3. Results and discussion the crossing of electrons from the cathode to the HTL
(Fig. 2b and c). In this way, the BCP layer (hole blocking
At ®rst, we prepared monolayer structures using TPD, layer: HBL) allows to con®ne the radiative recombinations
TNATA or NPB as ELs. These materials have blue emission in the HTL.
but their performances are very weak: low luminance and We used Alq3 and Bebq2 for the electron transport layer.
high voltage (Table 1). Insertion of PEDOT-PSS layer In the case of HTL/ETL system, we observed green emission
between the ITO and the EL allowed us to reduce threshold from the ETL, while the incorporation of BCP leads to blue
voltage and to increase the maximum luminance (Table 1). emission from the HTL (Fig. 2).
This additional layer protects the EL from oxygen or indium At ®rst, we studied TPD/BCP/Alq3 structure because Alq3
diffusion ITO [8] and improves the hole injection by low- is the most popular ETL and we optimised the thickness of
ering the energy barrier (0.5 versus 0.67 eV) between the each layer. The best result (Fig. 3) was obtained with the
highest occupied molecular orbital (HOMO) and ITO. The structure: TPD(60 nm)/BCP(15 nm)/Alq3(30 nm), the turn
on voltage was 5.9 V and the maximum luminance was
464 cd/m2 at 14.2 V.
Table 1
Performances of monolayer and bi-layer structures
Furthermore, on the energy diagram of this structure
(Fig. 2b), we noticed the large barrier in LUMO levels
Structures (nm) Vseuil (V) Lmax (cd/m2) VLmax …V† between Alq3 and BCP (0.7 eV). So, we used Bebq2
60 TNATA 6.4 82.0 16.8 instead of Alq3 because its LUMO energy is more suitable;
60 NPB 9.5 61.2 16.8 only a low energy barrier between Ca and Bebq2 (0.2 eV)
40 PEDOT ‡ 60 TNATA 3.3 240.0 8.4 and between Bebq2 and BCP (0.3 eV), for electron cross-
40 PEDOT ‡ 60 NPB 3.4 30.8 5.6
ing from the cathode to the HTL (Fig. 2c), the characteris-
40 PEDOT ‡ 60 TPD 4.7 7.2 10.2
tic L ˆ f …V† for TPD(60 nm)/BCP(15 nm)/Bebq2(20 nm)

Fig. 1. Molecular structures of the used organic materials.

 D. Troadec et al. / Synthetic Metals 127 (2002) 165±168 167

Fig. 2. Radiative recombination in: (a) TPD/Alq3, (b) TPD/BCP/Alq3 and (c) TPD/BCP/Bebq2 structures.

Fig. 3. L ˆ f …V† characteristics of TPD/BCP/Alq3 and TPD/BCP/Bebq2 structures.

Fig. 4. L ˆ f …V† characteristics of different NPB structures.

168 D. Troadec et al. / Synthetic Metals 127 (2002) 165±168

structure is shown in Fig. 3. On the one hand, we obtained led us to use Alq3 or Bebq2 layer to improve electron
higher luminance (about 700 cd/m2 at 14.6 V), and on the injection and transport, BCP layer to con®ne the radiative
other, higher threshold voltage (7.0 V). recombinations in the HTL and PEDOT-PSS to ameliorate
To reduce the voltage, we inserted PEDOT-PSS layer like hole injection. These modi®cations increase the luminance
for the ITO/TPD/Ca/Al structure. Then, for the PEDOT- from 82 cd/m2 at 16.8 V for ITO/TNATA/Ca/Al structure to
PSS/TPD/BCP/Alq3 structure, threshold voltage was redu- 5500 cd/m2 at 10.2 V for ITO/PEDOT-PSS/TNATA/BCP/
ced from 5.9 to 4.5 V and luminance was increased from Bebq2/Ca/Al structure, and at the same time threshold
464 cd/m2 at 14.2 V to 652 cd/m2 at 12.0 V. voltage is reduced from 6.4 to 2.5 V.
Finally, we studied PEDOT-PSS/TPD/BCP/Bebq2 struc-
ture with the two other HTL organic molecules (NPB and
TNATA) in place of TPD. These organic molecules are more
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