Study of thermal degradation of organic light emitting device structures by X-ray scattering

We report the process of thermal degradation of organic light emitting devices (OLEDs) having multilayered structure of [LiF/tris-(8-hydroxyquinoline) aluminum(Alq₃)/N,N′-Bis(naphthalen-1-yl)-N,N′-bis(phenyl)benzidine (NPB)/copper phthalocyanine (CuPc)/indium tin oxide (ITO)/SiO₂ on a glass] by synchrotron X-ray scattering. The results show that the thermally induced degradation process of OLED multilayers has undergone several evolutions due to thermal expansion of NPB, intermixing between NPB, Alq₃, and LiF layers, dewetting of NPB on CuPc, and crystallization of NPB and Alq₃ depending on the annealing temperature. The crystallization of NPB appears at 180 °C, much higher temperature than the glass transition temperature (T_g = 96 °C) of NPB. The results are also compared with the findings from the atomic force microscope (AFM) images.     

Light-emitting characteristics of organic light-emitting diodes with the MoOx-doped NPB and C60/LiF layer

The hole ohmic properties of the MoO_x-doped NPB layer have been investigated by analyzing the current density-voltage properties of hole-only devices and by assigning the energy levels of ultraviolet photoemission spectra. The result showed that the performance of organic light-emitting diodes (OLEDs) is markedly improved by optimizing both the thickness and the doping concentration of a hole-injecting layer (HIL) of N, N′-diphenyl-N, N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine (NPB) doped with molybdenum oxide (MoO_x) which was inserted between indium tin oxide (ITO) and NPB. For the doping concentration of above 25%, the device composed of a glass/ITO/MoO_x-doped NPB (100 nm)/Al structure showed the excellent hole ohmic property. The investigation of the valence band structure revealed that the p-type doping effects in the HTL layer and the hole concentration increased at the anode interfaces cause the hole-injecting barrier lowering. With both MoO_x-doped NPB as a hole ohmic contact and C₆₀/LiF as an electron ohmic contact, the device, which is composed of glass/ITO/MoO_x-doped NPB (25%, 5 nm)/NPB (63 nm)/Alq₃ (37 nm)/C₆₀ (5 nm)/LiF (1 nm)/Al (100 nm), showed the luminance of about 58,300 cd/m² at the low bias voltage of 7.2 V.     

Modification of optical and electrical properties of ITO using a thin Al capping layer

In this study, the work function, transmittance, and resistivity of indium tin oxide (ITO) thin films were successfully modified by depositing an Al capping layer on top of ITO with subsequent thermal annealing. The 5 nm thick Al layer was deposited by a conventional dc magnetron sputtering method and the layer was converted into an aluminum oxinitride by subjecting the sample to rapid thermal annealing (RTA) under a nitrogen atmosphere. The films exhibited a high transmittance of 86% on average within the visible wavelength region with an average resistivity value of 7.9 × 10^− 4 Ω cm. Heat-treating the Al/ITO films via RTA resulted in the decrease of the optical band gap from that of bare ITO. In addition, the films showed red-shift phenomena due to their decreased band gaps when the heat-treatment temperature was increased. The resultant electrical and optical characteristics can be explained by the formation of aluminum oxinitride on the surface of the ITO films. The work function of the heat-treated films increased by up to 0.26 eV from that of a bare ITO film. The increase of the work function predicts the reduction of the hole-injection barrier in organic light-emitting diode (OLED) devices and the eventual use of these films could provide much improved efficiency of devices.     

Photo- and electro-luminescent properties of 5,10,15,20-tetra-p-tolyl-21H,23H-porphine doped poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] films

In this work we studied both photoluminescence (PL) and electroluminescence (EL) properties of 5, 10, 15, 20-tetra-p-tolyl-21H, 23H-porphine (TTP) doped poly[2-methoxy-5-(2′-ethylhexyloxy)-1, 4-phenylenevinylene] (MEH-PPV) with the weight percentages of 0, 0.5, 1, 3, 5, 8 and 12, respectively. In the process of PL the significant energy transfer occurs from MEH-PPV to TTP, even though there is a small spectral overlap between the absorption of TTP and the emission of MEH-PPV. For investigation of the process of EL a series of organic light-emitting diodes were fabricated with the device structure of ITO/PEDOT:PSS/TTP-doped polymer layer/Al (ITO = Indium Tin Oxides; PEDOT:PSS = poly (3,4-oxyethyleneoxythiophene): poly-(styrene sulfonate)). In devices in which the TTP was present at 5% the emission of EL was dominated by TTP; at lower doping levels MEH-PPV emission dominated. Moreover, multi-color emission was observed at the doping level below 5%. On the other hand, the mechanism for the EL process was reported.     

Enhancement of green electroluminescence from 2,5-di-p-anisyl-isobenzofuran by double-layer doping strategy

A highly fluorescent compound, 2,5-di-p-anisyl-isobenzofuran (DABF), was synthesized and used as a dopant to fabricate efficient green electroluminescence (EL) devices. The highest occupied molecular orbital level of DABF suggests that it can be excited either by energy transfer or by direct charge trapping mechanism in the EL devices. Three kinds of devices were fabricated based on different emission mechanisms. A double-layer-doped device with DABF doped in both the hole-transporting layer and the electron-transporting layer of the ITO/NPB/TPBI/Mg:Ag device, where ITO is indium-tin-oxide, NPB is (4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl), and TPBI is (2,2′,2″-(1,3,5-benzenetriyl)tris[1-phenyl-1H-benzimidazole]), exhibited greatly enhanced brightness and efficiency comparing to the single-layer-doped devices. The brightness and efficiency enhancements are attributed to a combined contribution of energy transfer and direct charge trapping mechanisms in the double-layer-doped device.     

Synthesis and electroluminescent properties of blue-emitting t-butylated bis(diarylaminoaryl)anthracenes for OLEDs

A new series of blue fluorescent emitters based on t-butylated bis(diarylaminoaryl) anthracenes were synthesized and their electroluminescent properties investigated. Into these blue materials, t-butyl groups were introduced to both prevent molecular aggregation between the blue emitters through steric hindrance and reduce self-quenching. As such, this would contribute to overall improvement in OLED efficiency. To explore the electroluminescent properties of these materials, multilayered OLEDs were fabricated into a device structure of: ITO/NPB(50 nm)/blue emitters doped in ADN(30 nm)/Alq₃(20 nm)/Liq(2 nm)/Al(100 nm). All devices showed efficient blue emissions. In particular, one device exhibited highly efficient sky blue emissions with a maximum luminance of 11,060 cd/m² at 12.0 V and respective luminous and power efficiencies of 6.59 cd/A and 2.58 lm/W at 20 mA/cm². The peak wavelength of the electroluminescence was 468 nm with CIEx,y coordinates of (0.159, 0.198) at 12.0 V. In addition, a deep blue device with CIEx,y coordinates of (0.159, 0.151) at 12.0 V showed a luminous efficiency of 4.2 cd/A and power efficiency of 1.66 lm/W at 20 mA/cm².     

Structural, electrical and optical properties of ITO films with a thin TiO2 seed layer prepared by RF magnetron sputtering

Tin-doped indium oxide (ITO) films were deposited by RF magnetron sputtering on TiO₂-coated glass substrates (the TiO₂ layer is usually called seed layer). The properties of ITO films prepared at a substrate temperature of 300 °C on bare and TiO₂-coated glass substrates have been analyzed by using X-ray diffraction, atomic force microscope, optical and electrical measurements. Comparing with single layer ITO film, the ITO film with a TiO₂ seed layer of 2 nm has a remarkable 41.2% decrease in resistivity and similar optical transmittance. The glass/TiO₂ (2 nm)/ITO film achieved shows a resistivity of 3.37 × 10⁻⁴ Ω cm and an average transmittance of 93.1% in the visible range. The glass/TiO₂ may be a better substrate compared with bare glass for depositing high quality ITO films.     

Crystallization and electrical properties of ITO:Ce thin films for flat panel display applications

ITO and ITO:Ce films were deposited by DC magnetron sputtering using an ITO (SnO₂: 10 wt.%) target and CeO₂ doped ITO (CeO₂: 0.5, 3.0, 4.0 and 6.0 wt.%) ceramic targets, respectively, on unheated non-alkali glass substrates (corning E2000). The as-deposited films were annealed at 200 °C in an Ar atmosphere at a pressure of 1 Pa. The crystallization temperature of the ITO film was increased by introducing Ce atoms because they decrease the level of crystallinity. It was also confirmed that the etching rate, surface morphology and work function were improved by the addition of Ce atoms despite there being increased resistivity. The current voltage (I-V) characteristics of the OLED devices deteriorated with increasing Ce content in the ITO anode, which was attributed to a decrease in carrier density despite there being a high work function. Therefore, the carrier density is one of the most important factors that determine the turn-on voltage for OLED applications.     

Dielectric response of AlP by in-situ ellipsometry

We present and analyze pseudodielectric function data <ε> = <ε₁> + i<ε₂> of AlP from 0.75 to 5.05 eV. The sample is a 1.0 μm thick AlP film grown on (001) GaAs by molecular beam epitaxy (MBE). Spectroscopic ellipsometric data were obtained before removing the sample from the MBE chamber to avoid oxidation and related artifacts. Analysis of interference oscillations and corrections for overlayer effects with a multilayer parametric model yield the closest representation to date of the intrinsic bulk dielectric response ε of AlP. From this analysis we obtain the energies of the E₀′ and E₁ critical points of AlP.     

Electroluminescence of a device based on europium β-diketonate with phosphine oxide complex

Rare earth (RE) ions have spectroscopic characteristics to emit light in narrow lines, which makes RE complexes with organic ligands candidates for full color OLED (Organic Light Emitting Diode) applications. In particular, β-diketone rare earth (RE³⁺) complexes show high fluorescence emission efficiency due to the high absorption coefficient of the β-diketone and energy transfer to the central ion. In this work, the fabrication and the electroluminescent properties of devices containing a double and triple-layer OLED using a new β-diketone complex, [Eu(bmdm)₃(tppo)₂], as transporting and emitting layers are compared and discussed. The double and triple-layer devices based on this complex present the following configurations respectively: device 1: ITO/TPD (40 nm)/[Eu(bmdm)₃(tppo)₂] (40 nm)/Al (150 nm); device 2: ITO/TPD (40 nm)/[Eu(bmdm)₃(tppo)₂] (40 nm)/Alq₃ (20 nm)/Al (150 nm) and device 3: ITO/TPD (40 nm)/bmdm-ligand (40 nm)/Al (150 nm), were TPD is (N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1-biphenil-4,4-diamine) and bmdm is butyl methoxy-dibenzoyl-methane. All the films were deposited by thermal evaporation carried out in a high vacuum system. These devices exhibit high intensity photo- (PL) and electro-luminescent (EL) emission. Electroluminescence spectra show emission from Eu³⁺ ions attributed to the ⁵D₀ to ⁷F_J (J = 0, 1, 2, 3 and 4) transitions with the hypersensitive ⁵D₀ → ⁷F₂ transition (around 612 nm) as the most prominent one. Moreover, a transition from ⁵D₁ to ⁷F₁ is also observed around 538 nm. The OLED light emission was almost linear with the current density. The EL CIE chromaticity coordinates (X = 0.66 and Y = 0.33) show the dominant wavelength, λ_d = 609 nm, and the color gamut achieved by this device is 0.99 in the CIE color space.     

Organic light-emitting diodes with 2-(4-biphenylyl)-5(4-tert-butyl-phenyl)-1,3,4-oxadiazole layer inserted between hole-injecting and hole-transporting layers

Organic light-emitting diodes (OLEDs) were fabricated based on copper phthalocyanine (CuPc) (hole-injecting layer), N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) (hole-transporting layer) and tris(8-hydroxyquinoline) aluminum (Alq₃) (emission and electron-transporting layer). A 2-(4-biphenylyl)-5(4-tert-butyl-phenyl)-1,3,4-oxadiazole (PBD) layer was inserted between CuPc and NPB. The effect of different thickness of PBD layer on the performance of the devices was investigated. The device structure was ITO/CuPc/PBD/NPB/Alq₃/LiF/Al. Optimized PBD thickness was about 1 nm and the electroluminescent (EL) efficiency of the device with 1 nm PBD layer was about 48 percent improvement compared to the device without PBD layer. The inserted PBD layer improved charge carriers balance in the active layer, which resulted in an improved EL efficiency. The performance of devices was also affected by varying the thickness of NPB due to microcavity effect and surface-plasmon loss.     

Improvement of white organic light emitting diode performances by an annealing process

White organic light emitting diode (OLED) devices with the structure ITO/PHF:rubrene/Al, in which PHF (poly(9,9-di-n-hexylfluorenyl-2,7-diyl)) is used as blue light emitting host and rubrene (5,6,11,12-tetraphenylnapthacene) as an orange dye dopant, have been fabricated. Indium tin oxide (ITO) coated-glass and aluminium were used as anode and cathode, respectively. The devices were fabricated with various rubrene-dopant to obtain a white light emission. The OLED device that composed of several concentrations of rubrene-doped PHF film was prepared in this study. It was found that the concentration of rubrene in the PHF-rubrene thin film matrix plays a key role in producing the white color emission. In a typical result, the device composed of 0.06 wt.% rubrene-dopant produced the white light emission with the Commission Internationale de L'Eclairage (CIE) coordinate of (0.30,0.33). The turn-on voltage and the brightness were found to be as low as 14.0 V and as high as 6540 cd/m², respectively. The annealing technique at relatively low temperature (50 °C, 100 °C, and 150 °C) was then used to optimize the performance of the device. In a typical result, the turn-on voltage of the device could be successfully reduced and the brightness could be increased using the annealing technique. At an optimum condition, for example, annealed at 150 °C, the turn-on voltage as low as 8.0 V and the brightness as high as 9040 cd/m² were obtained. The mechanism for the improvement of the device performance upon annealing will be discussed.     

Improvement in the bias stability of zinc oxide thin-film transistors using Si3N4 insulator with SiO2 interlayer

The performance of ZnO thin film transistors (TFT) subjected to SiO₂ interlayer treatments on Si₃N₄ insulators was investigated. In the case of a SiO₂ interlayer of 10 nm on Si₃N₄ insulator, a drastic improvement in device performance was obtained. ZnO TFT with this interlayer showed reduced trap density between the Si₃N₄ and ZnO channel, bringing remarkable improvement in bias stability characteristics. These devices show good performance and exhibit a high field-effect mobility of 6.41 cm²/Vs, an on/off current ratio of 10⁸, and a subthreshold swing of 1.46 V/decade. Also, the turn-on voltage shifted from − 2 V to − 6 V with negligible changes in the subthreshold swing and field effect mobility after total stress time.     

Corrosion behavior of Al, Sc-co-doped ZnO thin films in 3.5% NaCl solution

The corrosion behavior of Al, Sc-co-doped zinc oxide films (with Sc-dopant varying in 0, 0.01, 0.13, 0.24 and 1.07 wt.% Sc) in 3.5% NaCl solution has been investigated. It was compared to that of the commercial indium tin oxide (ITO) thin film. The films were prepared by sputtering on the ZnO (4 N) target with RF and on the targets of Al (4 N), Al-0.4 wt.% Sc, Al-0.8 wt.% Sc, Al-1.7 wt.% Sc alloy and pure Sc with DC. The electrochemical studies revealed that the corrosion resistance of the films increases in the order AZO < Sc-doped AZO < ITO < annealed AZO (at 300 °C for 1 h). The AZO doped with higher Sc-content is more resistant to corrosion. Examining the surface morphology through atomic force microscope (AFM) and scanning electron microscope (SEM), the film, which is more susceptible to corrosion depicted a rougher surface. The electrical resistivity of the films maintained almost unchanged in 120-h test. However, the optical transmittance varied with the concentration of Sc-dopant in the films. The higher Sc-dopant in the film the more stable it is to maintain higher transmittance. Higher corrosion resistance for the Sc-doped AZO in comparison with the monotonic AZO is attributed to a release of lattice strain by the Sc (III)-dopant which its size is similar to Zn (II). The most corrosion-resistant specimen (i.e., Sc-doped AZO annealed at 300 °C for 1 h) is considered to have the complete release of the lattice strain.     

Studying trivalent/bivalent metal ion doped TiO2 as p-TiO2 in bipolar heterojunction devices

Trivalent/bivalent metal ions doped TiO₂ thin films (M_xTi_1−xO₂, M = Cr³⁺, Fe³⁺, Ni²⁺, Co²⁺, Mn²⁺ and x = 0.01, 0.05, 0.1, 0.15, 0.2) were deposited on Indium–tin oxide (ITO) coated glass substrates by spin coating technique. X-ray photoelectron spectroscopy (XPS) showed Ti⁴⁺ oxidation state of the Ti2p band in the doped p-TiO₂. The homogenous M_xTi_1−xO₂ was used to support n-ZnO thin films with thickness ∼40–80 nm and vertically aligned n-ZnO nanorods (NR) with length ∼300 nm and 1.5 μm. Current (I)–voltage (V) characteristics for the Ag/n-ZnO/M_xTi_1−xO₂/ITO/glass assembly showed rectifying behavior with small turn-on voltages (V₀) < 1 V. The ideality factor (η) and the resistances in both forward and reverse bias were calculated. The temperature dependence performance of these bipolar devices was performed and variation of the parameters with temperature was studied.     

基于N-苯基咔唑的红色有机电致发光材料

设计合成了一种N-苯基咔唑的衍生物:3-2-(3,3-二腈基亚甲基-5,5-二甲基-1-环己烯基)乙烯基-N-苯基-咔唑(PNCa-2CN).PNCa-2CN的甲醇溶液光致发光光谱和固体膜光致发光光谱峰值分别位于598nm和660nm.以PNCa-2CN作为红色发光材料掺杂在Alq3中,制备了结构为ITO/NPB/Alq3:PNCa-2CN(5%)/Alq3/Mg:Ag/Ag的具有较高发光效率的红色有机电致发光器件,器件的发光峰值为600nm,在外加20V直流电压时达到2372cd·m-2的发光亮度,100mA·cm-2和20mA·cm-2其亮度分别为323cd·m-2和64cd·m-2,器件最大流明效率达到1.3lm·W-1.     

White OLED using β-diketones rare earth binuclear complex as emitting layer

In this work, the fabrication and the characterization of a white triple-layer OLED using a β-diketones binuclear complex [Eu(btfa)₃phenterpyTb(acac)₃] as the emitting layer is reported. The devices were assembled using a heterojunction between three organic molecular materials: the N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)benzidine (NPB) as hole-transporting layer, the β-diketones binuclear complex and the tris(8-hydroxyquinoline aluminum) (Alq₃) as the electron transporting layer. All the organic layers were sequentially deposited under high vacuum environment by thermal evaporation onto ITO substrates and without breaking vacuum. Continuous electroluminescence emission was obtained varying the applied bias voltage from 10 to 22 V showing a wide emission band from 400 to 700 nm with about 100 cd/m² of luminance. The white emission results from a combined action between the binuclear complex, acting as hole blocking and emitting layer, blue from NPB and the typical Alq₃ green emission. The intensity ratio of the peaks is determined by the layer thickness and by the bias voltage applied to the OLED, allowing us to obtain a color tunable light source.     

Influence of electrochemical treatment of ITO surface on nucleation and growth of OLED hole transport layer

Indium-tin-oxide (ITO) surfaces were electrochemically treated with voltages from 0 to + 2.8 V in 0.1 M K₄P₂O₇ electrolyte. The initial growth mode of hole transport layer (HTL) was investigated by atomic force microscope (AFM) observation of thermally deposited 2 nm N,N-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) on the electrochemically treated ITO surfaces. The results showed that the morphology of NPB thin film was significantly influenced by the treating voltage via the change in surface energy, especially the polar component. The treatments with + 2.0 and + 2.4 V were found to be most effective for more uniform and denser nucleation of NPB. The influence of the electrochemical treatments on the nucleation and growth mode of HTL and therefore the device performance were discussed.     

Photoelectrochemical properties of nitrogen-doped indium tin oxide thin films prepared by reactive DC magnetron sputtering

Nitrogen-doped indium tin oxide (N-ITO) thin films are deposited on unheated ITO glass substrates in this study. The structural properties of the N-ITO thin films, determined by X-ray diffraction (XRD) and Raman scattering, show that the indium nitride (InN) phase is liable to form in N-ITO films prepared in 20% N₂. A broad XRD peak around 2θ = 33° and Raman peak around 490 cm^− 1 are assigned to the InN phase, but no such peak is observed from the ITO film. Hence, the bandgap is narrowed by N-doping for absorbing light of longer wavelengths of ~ 500 nm. However, under illumination by ultraviolet, the N-ITO film prepared in 20% N₂ exhibits the least photocurrent response, which is less than one third that of the N-ITO catalyst that was doped in 16.4% N₂. This result is attributed mostly to the fact that the valence and conduction band potentials are not positioned properly between the newly formed InN and host ITO phases, rendering inefficient inter-semiconductor electron transfer. Therefore, higher N-doped samples exhibit a lower photocurrent response. Interestingly, the N-ITO film prepared in 16.4% N₂ exhibits the highest photocurrent density of about 165.5 μA/cm² at an applied bias of 1.2 V. This implies that the N-ITO films should be prepared at a low N₂ ratio to ensure a favorable photoelectrochemical activity.     

Fabrication of low resistivity tin-doped indium oxide films with high electron carrier densities by a plasma sputtering method

Tin-doped indium oxide (ITO) films fabricated on glass substrates using a hot-cathode plasma sputtering method exhibited low resistivity of 9.7 × 10⁻⁵ Ω cm, which is due to a high carrier density of 2.1 × 10²¹ cm⁻³. The change in the number of carriers, N, as a function of film thickness d, strongly suggests that oxygen extraction in the initial stages of ITO film growth on the glass substrate surface, creates oxygen vacancies as an electron carrier source for improvement in the resistivity of the films.