Red organic light-emitting devices with dotted-line doped emitting layers

High efficiency red organic light-emitting devices (OLEDs) with several dotted-line doped layers (DLDLs) were fabricated by using an ultra-high vacuum organic molecular-beam deposition system. The red OLEDs consisted of indium-tin-oxide (ITO)/N, N′-diphenyl-N, N′-bis(1-naphthyl)-(1, 1′-biphenyl)-4, 4′-diamine (α-NPD): 40 nm/tris(8-hydroxyquinoline)aluminum (Alq₃)+4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetra-methyljuloldyl-9-enyl)-4H-pyran (DCJTB); 3%wt.: x nm/(Alq₃+DCJTB; 3%wt./ Alq₃)_n−1: (30−x) nm/ Alq₃: 30 nm/Mg:Ag with n of 2, 4, 6, or 8, and x=30/(2n−1). The luminance yield of the device with 8 DLDLs was 75% higher than that of the device with a common doped layer. This was attributed to more formation of the excitons formed in a wider region resulting from the existence of the DLDLs. The dominant mechanisms of the dopant emission for the devices with DLDLs were described on the basis of the sequential carrier trapping process.     

Spectroscopic ellipsometric characterization of organic films obtained via organic vapor phase deposition

Thin films of Tris(8-hydroxyquinoline)-aluminum(III) (Alq₃) and N,N-Di-[(1-naphthyl)-N,N-diphenyl]-(1,1-biphenyl)-4,4-diamine (-NPD ) were deposited on large-area silicon substrates by means of the recently developed organic vapor phase deposition (OVPD) method. Variable-angle spectroscopic ellipsometry was used to measure the optical constants of OVPD Alq₃ and -NPD layers in the 0.8–5 eV energy range. The absorption onset which defines the lower limit of the optical band gap was found to be at 2.65 eV and 2.9 eV for Alq₃ and -NPD , respectively. Additionally, the thicknesses of the layers as well as the thickness profiles of the organic thin films were determined along the 8 diameter of the wafers. The thickness analysis revealed large-area uniform deposition of the films. PACS 78.20.Ci; 81.70.Fy; 81.15.-z     

Diffusion study of multi-organic layers in OLEDs by ToF-SIMS

A model organic light-emitting diodes (OLEDs) with structure of tris(8-hydroxyquinoline) aluminum (Alq₃)/N,N′-diphenyl-N,N′-bis[1-naphthy-(1,1′-diphenyl)]-4,4′-diamine (NPB)/indium tin oxide (ITO)-coated glass was fabricated for diffusion study by ToF-SIMS. The results demonstrate that ToF-SIMS is capable of delineating the structure of multi-organic layers in OLEDs and providing specific molecular information to aid deciphering the diffusion phenomena. Upon heat treatment, the solidity or hardness of the device was reduced. Complicated chemical reaction might occur at the NPB/ITO interface and results in the formation of a buffer layer, which terminates the upper diffusion of ions from underlying ITO.     

Solution-processed white organic light-emitting devices based on small-molecule materials

We investigated solution-processed films of 4,4′-bis(2,2-diphenylvinyl)-1,1′-bibenyl (DPVBi) and its blends with N,N′-bis(3-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TPD) by atomic force microscopy (AFM). The AFM result shows that the solution-processed films are pin-free and their morphology is smooth enough to be used in OLEDs. We have developed a solution-processed white organic light-emitting device (WOLEDs) based on small-molecules, in which the light-emitting layer (EML) was formed by spin-coating the solution of small-molecules on top of the solution-processed hole-transporting layer. This WOLEDs, in which the EML consists of co-host (DPVBi and TPD), the blue dopant (4,4′-bis[2-(4-(N,N-diphenylamino)phenyl)vinyl]biphenyl) and the yellow dye (5,6,11,12-tetraphenylnaphtacene), has a current efficiency of 6.0 cd/A at a practical luminance of 1000 cd/m², a maximum luminance of 22500 cd/m², and its color coordinates are quite stable. Our research shows a possible approach to achieve efficient and low-cost small-molecule-based WOLEDs, which avoids the complexities of the co-evaporation process of multiple dopants and host materials in vacuum depositions.     

Color-tunable organic light-emitting devices using a thin N,N′-bis-(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine layer at heterojunction interface

Novel types of multilayer color-tunable organic light-emitting devices (OLEDs) with the structure of indium tin oxide (ITO)/N,N′-bis-(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB)/aluminum (III)bis(2-methyl-8-quinolinato)4-phenylphenolato (BAlq)/tris-(8-hydroxyquinolate)-aluminum (Alq₃)/Mg:Ag were fabricated. By inserting a thin layer with different thickness of a second NPB layer at the heterojunction interface of BAlq/Alq₃, the emission zone of devices shifted greatly and optoelectronic characteristics underwent large variation. Although BAlq was reported as a very good hole-blocking and blue-light-emission material, results of measurements in this paper suggested that a certain thickness of NPB layer between BAlq and Alq₃ plays an important role to modify device characteristics, which can act as recombination-controlling layer in the multilayer devices. It also provides a simple way to fabricate color-tunable OLEDs by just changing the thickness of this “recombination-controlling” layer rather than doping by co-evaporation.     

Bright electroluminescent devices with tunable spectra obtained by strictly controlling the doping concentration of electron injection sensitizer

In this paper, we report an efficient strategy to design bright blue and blue-green electroluminescent (EL) devices by slightly doping tris(8-hydroxyquinoline) aluminum (Alq₃) into N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-diphenyl-4,4′-diamine (NPB) as the light-emitting layer (EML). Bright EL devices with tunable spectra were obtained by strictly controlling the doping concentration of Alq₃. With increasing current density, EL efficiencies of these devices increase first and then decrease gradually after reaching the maximum. Analyzing the current density-voltage (J−V) characteristics of hole-only and electron-only devices, we found the presence of Alq₃ molecules in EML not only facilitates the injection of electrons from hole block layer (HBL) into EML but also stays the transport of holes in EML, thus causing significant enhancement of EL efficiency and brightness due to improved carriers balance and broadening of recombination zone. More interestingly, the doping concentration of Alq₃ strongly influences the injection and transport processes of electrons, thus determining the distribution of holes and electrons on NPB and Alq₃ molecules.     

Highly efficient yellow organic light-emitting diodes based on a hole-dominant host layer co-doped with yellow emitting and electron transporting guests

We fabricated high efficiency yellow-color organic light-emitting diodes (OLEDs) by co-doping 2,8-di(t-butyl)-5,11-di[4-(t-butyl)phenyl]-6,12-diphenylnaphthacene (TBRb) and tris(8-hydroxyquinolinato)aluminum (Alq₃) guests in a N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) host. Co-doping of electron-transporting Alq₃ with yellow dopant TBRb in hole-dominant NPB layers resulted in substantial luminance-yield improvement compared to TBRb-only counterparts without color contamination from Alq₃ green emission. The luminance yield of 11.4 cd/A, corresponding to the co-doping of 8% TBRb and 2% Alq₃, is larger than previously reported luminance-yield values of conventional TBRb-based yellow OLEDs. Another advantage of the TBRb-Alq₃ co-doped OLEDs is an insignificant roll-off of efficiency at high current-density and/or brightness levels.     

Effective barrier height and work function of Mg:Ag thin films with a low Mg concentration acting as cathodes in high-efficiency organic light emitting devices

Organic molecular-beam deposition (OMBD) of Mg:Ag thin films with a low Mg concentration on tris(8-hydroxyquinolino) aluminum (Alq₃) layers at room temperature was performed to investigate the feasibility of using Mg:Ag thin films as cathode electrodes in organic light-emitting devices (OLEDs). The effective barrier height of the Mg:Ag (5:95) thin films grown on the Alq₃ layers, determined from the current-voltage measurements, was as low as 0.22 eV. The work function of the Mg:Ag (5:95) thin film, determined from the secondary electron emission coefficients obtained by using focused ion beam, was 4.12 eV. These results indicate that Mg:Ag (5:95) thin films with a low Mg concentration grown by using the OMBD method hold promise for potential applications as cathode electrodes in high-efficiency OLEDs.     

Modification of anode surface in organic light-emitting diodes by chalcogenes

Influence of thin chalcogen X (S, Se, Te) interlayer between anode (indium-tin oxide, ITO) and a layer of N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD) used as a hole-transport layer (HTL) on the operating characteristics of organic light-emitting diodes (OLEDs) of composition ITO/X/TPD/Alq₃/Yb (Alq₃ - aluminum 8-quinolinolate) has been investigated. It was found that the sulphur layer decreases operating voltage and enhances operating stability of a device while the selenium or tellurium interlayers impair these characteristics.     

Photo- and electroluminescent properties of zinc(II) complexes with tetradentate Schiff bases,derivatives of salicylic aldehyde

It is studied how the introduction of various substituents into the composition of organic ligands affects the photoluminescence spectra of new zinc(II) complexes with tetradentate Schiff bases H₂L (derivatives of salicylic aldehyde (H₂SAL1, H₂SAL2) and o-vanillin (H₂MO1, H₂MO2) with ethylenediamine and o-phenylenediamine) in the form of bulk solids and thin films. It is demonstrated that the emission spectra of bulk solid complexes without o-phenylenediamine bridges (ZnSAL1 and ZnMO1) contain additional long-wavelength bands compared to the spectra of corresponding thin films. In the case of films obtained from [ZnSAL1]₂ dimer complexes, the long-wavelength band is dominant. At the same time, the photoluminescence spectra of ZnSAL2 and ZnMO2 complexes with o-phenylenediamine bridges are similar in the case of solid samples and thin films. The electroluminescent properties of organic light-emitting diodes (OLEDs) with the ITO/α-NPD/ZnL/Ca:Al structure are studied. The bathochromic shift of the electroluminescence peaks of OLEDs with respect to the photoluminescence spectra of bulk solid samples and thin films is probably related to the formation of exciplexes at the α-NPD/ZnL interface. The electroluminescence spectra of OLEDs based on [ZnSAL1]₂ show a hypsochromic shift of the emission maximum, which can be caused by a shift of the recombination region into the α-NPD layer.     

Enhanced brightness of organic light-emitting diodes based on Mg:Ag cathode using alkali metal chlorides as an electron injection layer

Different thicknesses of cesium chloride (CsCl) and various alkali metal chlorides were inserted into organic light-emitting diodes (OLEDs) as electron injection layers (EILs). The basic structure of OLED is indium tin oxide (ITO)/N,N′-diphenyl-N,N′-bis(1-napthyl-phenyl)-1.1′-biphenyl-4.4′-diamine (NPB)/tris-(8-hydroxyquinoline) aluminum (Alq₃)/Mg:Ag/Ag. The electroluminescent (EL) performance curves show that both the brightness and efficiency of the OLEDs can be obviously enhanced by using a thin alkali metal chloride layer as an EIL. The electron injection barrier height between the Alq₃ layer and Mg:Ag cathode is reduced by inserting a thin alkali metal chloride as an EIL, which results in enhanced electron injection and electron current. Therefore, a better balance of hole and electron currents at the emissive interface is achieved and consequently the brightness and efficiency of OLEDs are improved.     

Improved performance of organic light-emitting devices with plasma treated ITO surface and plasma polymerized methyl methacrylate buffer layer

Transparent indium-tin-oxide (ITO) anode surface was modified using O₃ plasma and organic ultra-thin buffer layers were deposited on the ITO surface using 13.56 MHz rf plasma polymerization technique. A plasma polymerized methyl methacrylate (ppMMA) ultra-thin buffer layer was deposited between the ITO anode and hole transporting layer (HTL). The plasma polymerization of the buffer layer was carried out at a homemade capacitively coupled plasma (CCP) equipment. N,N′-Diphenyl-N,N′-bis(3-methylphenyl)-1,1′-diphenyl-4,4′-diamine (TPD) as HTL, Tris(8-hydroxy-quinolinato)aluminum (Alq₃) as both emitting layer (EML)/electron transporting layer (ETL), and aluminum layer as cathode were deposited using thermal evaporation technique. Electroluminescence (EL) efficiency, operating voltage and stability of the organic light-emitting devices (OLEDs) were investigated in order to study the effect of the plasma surface treatment of the ITO anode and role of plasma polymerized methyl methacrylate as an organic ultra-thin buffer layer.     

Effect of desiccant on the performance of green organic light-emitting device

A green organic light-emitting diodes (OLED) with a multilayer structure of indium-tin oxide (ITO)/copper-phthalocyanine (CuPc) (200Å)/N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (α-NPD) (600Å)/N′- diphenyl-N,N′-tris(8-hydroxyquinoline) aluminium (Alq₃) (400Å):10-(2-benzothiazolyl)-1,1,7,7-tetramethyl-2,3,6,7- tetrahydro-1H,5H,11H-(l)benzopyropyrano(6,7,8-i, j)quinolizin-11-one (C545T) (2%)/Alq₃ (200Å)/LiF (10Å)/Al (1000Å) was prepared via vacuum thermal evaporation. To reduce the impact of water vapor and oxygen on the device, we encapsulated it with a kind of specific and efficient desiccant, called DESIPASTE, under the protection of high-purity nitrogen. By analyzing a series of optical characteristics of OLEDs, the results showed that this desiccant can improve the brightness about 500 and 250 cd/m² at same driving voltage and current density, respectively. The electroluminescent (EL) spectra were hardly affected except a very weak blue shift of broadband emission peak. It turns out that encapsulation with DESIPASTE is a simple and efficient way to improve the performance of OLED.     

Performance improvement of rubrene-based organic light emitting devices with a mixed single layer

We have investigated the performance of organic light-emitting devices (OLEDs) with a rubrene-doped mixed single layer by using 4,4′-bis[N-(1-napthyl)-N-phenyl- amion] biphenyl (α-NPD) as hole transport layer. Comparing to a conventional heterostructure OLED, equal luminance vs. current density characteristics were obtained. In addition, maximum power efficiency was threefold improved, and the achieved value was 5.90 lm/W by optimizing a mixing ratio of hole and electron transport materials. By evaluating the temperature dependence of the J – V characteristics for electron-injection dominated device, the electron injection from Al/LiF to mixed organic layer is attributed to Schottky thermal emission model. And the barrier height of the electron injection from Al/LiF into mixed single layer was obtained to be 0.62 eV, which is lower than Al/Alq₃ interface. Meanwhile, the mixed single-layer device exhibited superior operational durability at a half-luminance of 2,250 h under a constant current operation mode. The reliability was improved with a factor of two compared to the heterostructure device due to the improvement of stability in mixed organic molecules and removal of the heterojunction interface in the mixed single-layer device.     

亚单层黄色有机发光器件制备与光电性能研究

采用掺杂薄层作为亚单层有机发光技术,利用沉积在有机发光器件发光层中的亚单层分子[2-methyl-6-[2-(2,3,6,7-tetrahydro-1H,5H-benzo[ij] quinolizin-9-yl) ethenyl]-4H-pyran-4-ylidene] propane-dinitrile （DCM2）作为探针,同时改变DCM2层的位置,制备了四种亚单层结构的有机发光器件,对有机发光器件中激子的形成与扩散进行了研究,通过对各器件不同条件下的电致发光谱、发光强度和发光效率的对比研究,得到在N,N′-bis-(1-naphthyl)-N,N′-diphenyl-1,1′-biph-enyl-4,4′-diamine（NPB）/(8-hydroxyquinoline) aluminium（Alq）异质结界面处引入亚单层DCM2可以使DCM2分子获得的激子数量最多,获得了高效率的黄色有机发光器件.从其中总结规律,对有机发光器件制作有一定的指导作用.     

Probing electric field distribution in organic double-layer diode by electric field induced optical second harmonic generation

Analyzing spectroscopic optical properties of an organic double-layer diode comprised of α-NPD and Alq₃ layers, we studied the selectively probing of electric field distribution in one of the two layers by using the microscopic electric field induced optical second harmonic generation (EFISHG) measurement. Spectroscopic SHGs from Indium–Zinc-Oxide/N,N-Di(naphthalene-1-yl)-N,N′-diphenyl-benzidine/tris(8-quinolinolato) aluminium/Al (IZO/α-NPD/Alq₃/Al) diodes were measured. Results showed that the SHG peaks were generated at 940 and 1050 nm from the α-NPD and Alq₃ layers, respectively, due to the EFISHG process, and the electric field in each layer can be selectively probed. The contribution of the accumulated charge at the double-layer α-NPD and Alq₃ interface was also identified by the d.c. voltage dependence on the EFISHG intensity.     

Exciplex or electroplex emissions from the interface between aromatic diamine and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline?

Organic light-emitting diodes (OLEDs) have been fabricated which consist of N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine) (TPD), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), and tris(8-hydroxyquinoline) aluminum (Alq₃). Four emission peaks located at about 401 nm, 425 nm, 452 nm and 480 nm have been obtained in the electroluminescence (EL) spectra of these devices. The former two emissions originate from the exciton emission of TPD molecular. The last two emissions could be attributed to local (LOC) exiplex emission and charge transfer (CT) exiplex emission at the interface between TPD and BCP layers, respectively.     

UV–VIS and mid-IR ellipsometer characterization of layers used in OLED devices

We report on the analysis of layer materials commonly used for the fabrication of organic light-emitting diodes (OLEDs) by means of spectroscopic ellipsometry operating in the ultraviolet–visible (UV–VIS) and in the mid-infrared (mid-IR) range of the electromagnetic spectrum. On covering a wide spectral range, these non-destructive, non-contact techniques offer a huge potential in characterizing thin films in terms of layer thickness values, optical indices, absorption properties modified by incorporating optically active dopant molecules, and, finally, electrical layer properties. Individual absorption bands of single organic films can significantly affect the luminance and performance efficiency of OLEDs when building multi-layer stacks. Using mid-IR spectroscopic ellipsometry, the resistance of as-deposited and annealed indium–tin oxide (ITO) layers on glass is determined and compared with values obtained by four-point probe techniques.     

Electroluminescence performance of organic light-emitting devices with KCl inside hole transport layer

A new multilayer organic light-emitting device (OLED) is fabricated by inserting kalium chloride (KCl) thin layer (1 nm) into hole transport layer (HTL). It has the configuration of ITO/NPB(15 nm)/KCl(1 nm)/NPB(25 nm)/Alq₃(60 nm)/KCl(1 nm)/Al. The electroluminescence (EL) result shows that the performance of the novel device has obviously improvement compared with the normal structure (ITO/NPB(40 nm)/Alq₃(60 nm)/KCl(1 nm)/Al). The EL and efficiency are about 1.4 and 1.3 times than that of conventional device. The suggested mechanism is that the KCl layer in N,N′-diphenyl-N,N′-bis(1-napthyl–phenyl)-1,1′-biphenyl-4,4′-diamine (NPB) can block the holes of NPB and then balance the holes and electrons. The better recombination of holes and electrons is beneficial to the enhancing properties of OLED.     

Emission properties of dopants rubrene and coumarin 6 in Alq3 films

We have investigated the emission properties of dopants 5,6,11,12-tetraphenylnapthacene (rubrene) and 3-(2′-benzothiazolyl)-7-diethylaminocoumarin (coumarin 6) as well as co-doping of these two dopants in tris (8-hydroxyquinolinato) aluminum (Alq₃) films in double-layer organic light emitting diodes (OLEDs). We varied the rubrene (Rb) doping concentration in Alq₃:Rb films up to 10 wt%. The maximum luminescence efficiency of ∼6.5 cd/A was observed for Rb doping concentration of ∼0.7 wt% in Alq₃:Rb film, which was nearly double efficiency compared to pure Alq₃ device. The co-doping of dopants of C-6 and Rb in the ratio of 1:1 and 1:2 in Alq₃ films reduced the bias voltage compared to pure Alq₃ and Alq₃:C-6 devices for the same current density. The maximum luminescence efficiency was improved to ∼7 cd/A in Alq₃:{C-6:Rb(1:2)} film OLED. The direct recombination of holes and electrons in the dopant molecules may be responsible for the improvement of the luminescence efficiency. We also observed the shifting of photoluminescence (PL) and electroluminescence (EL) peaks position from ∼515 to ∼562 nm by co-doping of Rb and C-6 in Alq₃.