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.     

Enhanced performance of the OLED with plasma treated ITO and plasma polymerized thiophene buffer layer

In this work, indium-tin-oxide (ITO) electrode in organic light emitting device (OLED) was modified by using an O₂ plasma treatment and plasma polymerized thiophene buffer layers were inserted between ITO (anode) and organic layer in order to improve the hole injection efficiency. Furthermore, electron injection to cathode (Al) in the test OLED seemed to be improved due to introduction of quantum well in the cathode. The plasma-polymerized thiophene buffer layer on the O₂ plasma-treated transparent ITO electrode seemed to result in formation of a stable interface and consequently, reduction the hole mobility, which in turn caused enhanced recombination of hole and electron in the emitting layer. Compared with the test device without buffer layer, the turn-on voltage of the test device with the buffer layer was lowered by 1.0 V.     

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.     

Influence of the deposition temperature on the structure and performance of tris(8-hydroxyquinoline) aluminum based flexible organic light-emitting devices

Based on indium tin oxide (ITO)/N,N′diphenyl-N-N′-di(m-tdyl) benzidine (TPD)/Alq₃/Al structure, flexible OLEDs on polyethylene terephthalate (PET) substrates were fabricated by physical vapor deposition (PVD) method. Tris(8-hydroxyquinoline)aluminum (Alq₃) films were deposited at 90, 120 and 150 °C to examine the influence of the deposition temperature on the structure and performance of OLEDs. Electroluminescence (EL) spectra and current-voltage-luminance (I-V-L) characteristics of the OLEDs were examined. It was found that the device fabricated at a high temperature had a higher external efficiency and longer lifetime. Atomic force microscope (AFM) was adopted to characterize the surface morphology of ITO/TPD/Alq₃. The higher uniform morphology of the Alq₃ formed at high temperature might contribute to the performance improvement of the OLEDs.     

On the improvement of the electroluminescent signal of organic light emitting diodes by the presence of an ultra‐thin metal layer at the interface organic/ITO

The electroluminescent (EL) signal of organic light emitting diodes (OLEDs) based on simple “hole transporting layer/electron transporting layer” (HTL/ETL) structures has been studied as a function of the anode/HTL interface, the anode being an indium tin oxide (ITO) film. It is shown that the electroluminescent (EL) signal increases when a metal ultra‐thin layer is introduced between the anode and the HTL. Experimental results show that the work function value of the metal is only one of the factors which allow improving the EL signal via better hole injection efficiency. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Modification of the organic/La0.7Sr0.3MnO3 interface by in situ gas treatment

La_0.7Sr_0.3MnO₃ (LSMO) can act as a spin injection electrode in organic spin-valves and organic light-emitting devices. For the latter application, good control of the electronic structure of the organic/LSMO interface is a key issue to ensure sufficient current injection in the device. By exposing cleaned LSMO surfaces to activated oxygen and hydrogen, the work function of the samples can reach 5.15 and 4.3 eV, respectively, as shown by in situ photoemission measurements. The initial stage of formation of the organic/LSMO interface upon deposition of N,N′-bis-(1-naphyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) onto the oxygen-treated LSMO surface is examined. We find that the NPB molecules evenly cover the LSMO surface and that the interface barrier height is 0.8 eV, which is comparable to that at the NPB/indium tin oxide (ITO) interface with the ITO surface pretreated in situ by oxygen plasma.     

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.     

Surface modification of indium tin oxide anode with self-assembled monolayer modified Ag film for improved OLED device characteristics

Modification of electrodes has attracted much attention in the study of organic semiconductor devices. A self-assembled monolayer (SAM) of 4-fluorothiophenol is employed to modify the Ag film on the surface of indium tin oxide (ITO) to improve the hole injection and the surface morphology. The modified anode was characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), and UV–vis transmittance spectra. To investigate the effect of the modification on the device characteristics, typical double layer devices with the structure of anode/-naphthylphenylbiphenyl diamine (NPB, 60 nm)/tris-(8-hydroxyquinoline) aluminum (Alq₃, 60 nm)/LiF(0.7 nm)/Al(100 nm) were fabricated using the modified anode and the bare ITO. The effect of Ag layer thickness on the device performance is also investigated. The results revealed that SAM modified ultra-thin Ag film is an effective buffer layer for organic light emitting diode. The device using the ITO/Ag (5 nm)/SAM as anode show improved device characteristics than that of using bare ITO as anode. The enhancements in luminance and efficiency are attributed to enhanced hole injection and smooth surface between anode and the organic material. The Ag thickness of 5 nm is chosen as an acceptable compromise between substrate transparency and the device performance.     

Ultraviolet photoelectron spectroscopy investigation of interface formation in an indium-tin oxide/fluorocarbon/organic semiconductor contact

It has been demonstrated that hole-injection in organic light-emitting devices (OLEDs) can be enhanced by inserting a UV-illuminated fluorocarbon (CF_x) layer between indium-tin oxide (ITO) and organic hole-transporting layer (HTL). In this work, the process of interface formation and electronic properties of the ITO/CF_x/HTL interface were investigated with ultraviolet photoelectron spectroscopy. It was found that UV-illuminated fluorocarbon layer decreases the hole-injection barrier from ITO to α-napthylphenylbiphenyl diamine (NPB). Energy level diagrams deduced from the ultraviolet photoelectron spectroscopy (UPS) spectra show that the hole-injection barrier in ITO/UV-treated CF_x/NPB is the smallest (0.46 eV), compared to that in the ITO/untreated CF_x/NPB (0.60 eV) and the standard ITO/NPB interface (0.68 eV). The improved current density-voltage (I-V) characteristics in the UV-treated CF_x-coated ITO contact are consistent with its smallest barrier height.     

Two peaks observed in the electroluminescence spectra of Alq3-based OLEDs

Tris(8-hydroxyquinolato) aluminum (Alq₃)-based organic light-emitting diodes were fabricated with or without using a hole transport layer (HTL). As a conventional device, the ITO/Alq₃/Mg-Ag device yielded a green-light emission with a single peak at 525 nm in the electroluminescence (EL) spectrum. In contrast, two sub-peaks were observed in the EL spectrum of some ITO/HTL/Alq₃/Mg-Ag devices. This difference was tentatively explained by comparing EL with the photoluminescence (PL) spectrum reported in the literature.     

The roles of zinc selenide sandwiched between organic layers and its applications in white light-emitting diodes

In this paper, the roles of zinc selenide (ZnSe) sandwiched between organic layers, i.e. organic/ZnSe/aluminum quinoline (Alq₃), have been studied by varying device structure. A broad band emission was observed from ITO/poly(N-vinylcarbazole)(PVK)(80 nm)/ZnSe(120 nm)/ Alq₃(15 nm)/Al under electric fields and it combined the emissions from the bulk of PVK, ZnSe and Alq₃, however, emission from only Alq₃ was observed from trilayer device ITO/N,N^′-bis-(1-naphthyl)-N,N^′-diphenyl-1, 1^′-biphenyl-4, 4^′-diamine (NPB) (40 nm)/ZnSe(120 nm)/ Alq₃(15 nm)/Al. Consequently the luminescence mechanism in the ZnSe layer is suggested to be charge carrier injection and recombination. By thermal co-evaporating Alq₃ and 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB), we get white light emission with a Commission Internationale de l’E clairage (C.I.E) co-ordinates of (0.32, 0.38) from device ITO/PVK(80 nm)/ZnSe(120 nm)/ Alq₃:DCJTB(0.5 wt% DCJTB)(15 nm)/Al at 15 V and the device performs stably with increasing applied voltages.     

Electrical characteristics and efficiency of organic light-emitting diodes depending on hole-injection layer

In a device structure of ITO/hole-injection layer/N,N′-biphenyl-N,N′-bis-(1-naphenyl)-[1,1′-biphthyl]4,4′-diamine(NPB)/tris(8-hydroxyquinoline)aluminum(Alq₃)/Al, we investigated the effect of the hole-injection layer on the electrical characteristics and external quantum efficiency of organic light-emitting diodes. Thermal evaporation was performed to make a thickness of NPB layer with a rate of 0.5–1.0 Å/s at a base pressure of 5 × 10⁻⁶ Torr. We measured current–voltage characteristics and external quantum efficiency with a thickness variation of the hole-injection layer. CuPc and PVK buffer layers improve the performance of the device in several aspects, such as good mechanical junction, reducing the operating voltage, and energy band adjustment. Compared with devices without a hole-injection layer, we found that the optimal thickness of NPB was 20 nm in the device structure of ITO/NPB/Alq₃/Al. By using a CuPc or PVK buffer layer, the external quantum efficiencies of the devices were improved by 28.9% and 51.3%, respectively.     

Implementation of anti-reflection coating to enhance light out-coupling in organic light-emitting devices

We report significant enhancement of light out-coupling in organic light-emitting devices (OLEDs) by means of anti-reflection coating of magnesium fluoride (MgF₂) on the backside of glass substrate. OLEDs were fabricated by employing the green electrophosphorescent material fac tris-(2-phenylpyridine) iridium [Ir(ppy)₃] doped in 4,4′,8-N,N-8-dicarbazole-biphenyl (CBP) and 0.4 wt% tetrafluorotetracyano-quinodimethane (F4-TCNQ)-doped naphthylphenylbiphenyl diamine (α-NPD) as hole transport layer (HTL). Single-layer MgF₂ with the thickness of λ/4 was then vacuum deposited on the backside of glass substrate of OLED. About two-fold enhancement in luminance with anti-reflection coating of MgF₂ has been observed.     

Reduction of driving voltage in organic light-emitting diodes with molybdenum trioxide in CuPc/NPB interface

A novel structure of organic light-emitting diode was fabricated by inserting a molybdenum trioxide (MoO₃) layer into the interface of hole injection layer copper phthalocyanine (CuPc) and hole transport layer N,N′-diphenyl-N,N′-bis(1-napthyl-phenyl)-1,1′-biphenyl-4,4′-diamine (NPB). It has the configuration of ITO/CuPc(10 nm)/MoO₃(3 nm)/NPB(30 nm)/ tris-(8-hydroxyquinoline) aluminum (Alq₃)(60 nm)/LiF(0.5 nm)/Al. The current density-voltage-luminance (J-V-L) performances show that this structure is beneficial to the reduction of driving voltage and the enhancement of luminance. The highest luminance increased by more than 40% compared to the device without hole injection layer. And the driving voltage was decreased obviously. The improvement is ascribed to the step barrier theory, which comes from the tunnel theory. The power efficiency was also enhanced with this novel device structure. Finally, “hole-only” devices were fabricated to verify the enhancement of hole injection and transport properties of this structure.     

Stable organic solar cells employing MoO3-doped copper phthalocyanine as buffer layer

A stable organic solar cell with structure of ITO/buffer/donor/acceptor/cathode is presented. A thin layer (5 nm) of MoO₃-doped CuPc is adopted as the buffer in CuPc/C₆₀ organic heterojunction photovoltaic (PV) solar cells, resulting in two times longer lifetime. The surface morphology of buffer layer plays a decisive role in improving the stability.     

Pure blue emission from undoped organic light emitting diode based on anthracene derivative

This paper presents organic light emitting diodes (OLEDs) which were fabricated by using undoped 9,10-di(2-naphthyl)anthracene (ADN) as the emitting layer, N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-amine (TPD) as the hole transporting layer, and one of tris-(8-hydroxy-quinolinato) aluminum (Alq₃), 4,7-diphenyl-1,10-phenanthroline (Bphen) and 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole (PBD) as the electron transporting layer. By optimization for the thickness of device, efficient pure blue organic light emitting diodes were obtained, which is attributed to the synergy of both the hole transporting layer and the electron transporting layer.     

Optical properties of ITO/TiO2 single and double layer thin films deposited by RPLAD

Indium tin oxide (ITO) and titanium dioxide (TiO₂) single layer and double layer ITO/TiO₂ films were prepared using reactive pulsed laser ablation deposition (RPLAD) with an ArF excimer laser for applications in dye-sensitized solar cells (DSSCs). The films were deposited on SiO₂ substrates either at room temperatures (RT) or heated to 200-400 °C. Under optimized conditions, transmission of ITO films in the visible (vis) range was above 89% for films produced at RT and 93% for the ones deposited at higher temperatures. Increasing the substrate temperature from RT to 400 °C enhances the transmission of TiO₂ films in the vis-NIR from about 70% to 92%. High transmission (≈90%) was observed for the double layer ITO/TiO₂ with a transmission cut-off above 900 nm. From the transmission data, the energies gaps (E_g), as well as the refractive indexes (n) for the films were estimated. n ≈ 2.03 and 2.04, respectively for ITO films and TiO₂ film deposited at 400 °C in the visible region. Post-annealing of the TiO₂ films for 3 h at 300 and 500 °C was performed to enhance n. The refractive index of the TiO₂ films increases with the post-annealing temperature. The direct band gap is 3.6, 3.74 and 3.82 eV for ITO films deposited at RT, 200, and 400 °C, respectively. The TiO₂ films present a direct band gap of 3.51 and 3.37 eV for as deposited TiO₂ films and when annealed at 400 °C, respectively. There is a shift of about 0.1 eV between ITO and ITO/TiO₂ films deposited at 200 °C. The shift decreases by half when the TiO₂ film was deposited at 400 °C. Post-annealing was also performed on double layer ITO/TiO₂.     

New double graded structure for enhanced performance in white organic light emitting diode

This study presents a new design that uses a combination of a graded hole transport layer (GH) structure and a gradually doped emissive layer (GE) structure as a double graded (DG) structure to improve the electrical and optical performance of white organic light-emitting diodes (WOLEDs). The proposed structure is ITO/m-MTDATA (15 nm)/NPB (15 nm)/NPB: 25% BAlq (15 nm)/NPB: 50% BAlq (15 nm)/BAlq: 0.5% Rubrene (10 nm)/BAlq: 1% Rubrene (10 nm)/BAlq: 1.5% Rubrene (10 nm)/Alq₃ (20 nm)/LiF (0.5 nm)/Al (200 nm). (m-MTDATA: 4,4′,4″ -tris(3-methylphenylphenylamino)triphenylamine; NPB: N,N′-diphenyl-N,N′-bis(1-naphthyl-phenyl)-(1,1′-biphenyl)-4,4′-diamine; BAlq: aluminum (III) bis(2-methyl-8-quinolinato) 4-phenylphenolate; Rubrene: 5,6,11,12-tetraphenylnaphthacene; Alq₃: tris-(8-hydroxyquinoline) aluminum). By using this structure, the best performance of the WOLED is obtained at a luminous efficiency at 11.8 cd/A and the turn-on voltage of 100 cd/m² at 4.6 V. The DG structure can eliminate the discrete interface, and degrade surplus holes, the electron-hole pairs are efficiently injected and balanced recombination in the emissive layer, thus the spectra are unchanged under various drive currents and quenching effects can be significantly suppressed. Those advantages can enhance efficiency and are immune to drive current density variations.     

Atomic force microscopy investigation of surface roughness generated between SiO2 micro-pits in CHF3/Ar plasma

The present paper investigates the surface roughness generated by reactive ion etching (RIE) on the location between silicon dioxide (SiO₂) micro-pits structures. The micro-pit pattern on polymethyl methacrylate (PMMA) mask was created by an electron beam lithography tool. By using PMMA as a polymer resist mask layer for pattern transfer in RIE process, the carbon (C) content in etching process is increased, which leads to decrease of F/C ratio and causes domination of polymerization reactions. This leads to high surface roughness via self-organized nanostructure features generated on SiO₂ surface which was analyzed using atomic force microscopy (AFM) technique. The etching chemistry of CHF₃ plasma on PMMA masking layer and SiO₂ is analyzed to explain the polymerization. The surface root-mean-square (RMS) roughness below 1 nm was achieved by decreasing the RF power to 150 W and process pressure lower than 10 mTorr.     

Plasma treatment of ITO surfaces to improve luminescence characteristics of organic light-emitting devices with dopants

Indium-tin-oxide (ITO) surfaces were treated with O₂ and H₂ plasmas. The contact angle of water, X-ray photoelectron spectroscopy (XPS) spectra, and luminescence characteristics of organic light-emitting devices (OLEDs) fabricated on plasma-treated ITO surfaces using poly(N-vinylcarbazole) (PVK) films doped with 5,6,11,12-tetraphenylnaphthacene (rubrene) or Nile Red were investigated.Using O₂ plasma treatment, the contact angle was reduced from 35° to 13°. The luminance of OLEDs with rubrene was significantly improved. The luminous color of an OLED inserted poly (3,4-ethylenedioxythiophene)-polystyrene sulphonic acid (PEDOT-PSS) layer between Nile Red-doped PVK film and O₂-plasma-treated ITO surface turned white as the applied voltage increased.