Highly efficient greenish blue-emitting organic diodes based on pyrene derivatives

We report the synthesis of pyrene derivatives as the light emissive layer for highly efficient organic electroluminescence (EL) diodes. Multilayer devices were fabricated with pyrene derivatives (ITO/NPB (50 nm)/blue material (30 nm)/BCP (10 nm)/Alq₃ (30 nm)/LiF (1 nm)/Al). By using 1,1′-dipyrene (DP) and 1,4-dipyrenyl benzene (DPB), the devices produced the blue EL emissions with 1931 Commission International de L’Eclairage coordinates of (x=0.21, y=0.35) and (x=0.19, y=0.25), respectively. The device with DPB shows a maximum brightness of 42,445 cd/m² at 400 mA/cm² and the luminance efficiency of 8.57 cd/A and 5.18 lm/W at 20 mA/cm².     

White organic electroluminescence from fluorescent bis (2-(2-hydroxyphenyl) benzoxazolate)zinc doped with phosphorescent material

Efficient white electroluminescence has been obtained by using an electroluminescent layer comprising of a blue fluorescent bis (2-(2-hydroxyphenyl) benzoxazolate)zinc [Zn(hpb)₂] doped with red phosphorescent bis (2-(2′-benzothienyl) pyridinato-N,C^3′)iridium(acetylacetonate) [Ir(btp)₂acac] molecules. The color coordinates of the white emission spectrum was controlled by optimizing the concentration of red dopant in the blue fluorescent emissive layer. Organic light-emitting diodes were fabricated in the configuration ITO/α-NPD/Zn(hpb)₂:0.01 wt%Ir(btp)₂acac/BCP/Alq₃/LiF/Al. The J-V-L characteristic of the device shows a turn on voltage of 5 V. The electroluminescence (EL) spectra of the device cover a wide range of visible region of the electromagnetic spectrum with three peaks around 450, 485 and 610 nm. A maximum white luminance of 3500 cd/m² with CIE coordinates of (x, y=0.34, 0.27) at 15 V has been achieved. The maximum current efficiency and power efficiency of the device was 5.2 cd/A and 1.43 lm/W respectively at 11.5 V.     

White organic electroluminescent device with photovoltaic performances

Organic device with structure of indium tin oxide (ITO)/1,3,5-tris-(3-methylphenylphenylamino)triphenylamine (m-MTDATA)/2-tert-butyl-9,10-di-beta-naphthylanthracene (TBADN)/2,9-dimethyl-4,7-diphenyl-1,10-phenan-throline (BCP)/LiF/Al, was fabricated, which show high efficient white electroluminescence (EL) or photovoltaic (PV) properties when it was driven by direct current (DC) bias or illuminated by ultraviolet (UV) light. Under a DC bias, the device shows efficient white EL emission. A maximum luminous efficiency of 1.1 lm/W was obtained at 8 V, which corresponds the Commission International de L’Eclairage coordinates (CIE) of (x = 0.298, y = 0.365). When the bias was increased to 12 V, the device shows bright white emission with the maximum brightness of 4300 cd/m², corresponding CIE coordinates of (x = 0.262, y = 0.280). When the diode was irradiated by a 365 nm UV-light (4 mW/cm²), the open-circuit voltage (V_oc) of 1.2 V, short-circuit (I_sc) of 0.065 mA/cm², fill factor (FF) of 0.24 and power conversion efficiency of 0.47% have been determined, respectively. The generation mechanisms of white light and PV of the bi-functional diode were discussed as well.     

Efficient white organic light-emitting devices using 4,7-diphenyl-1,10-phenanthroline as block layer

A white light-emitting device has been fabricated with a structure of ITO/m-MTDATA (45 nm)/NPB (10 nm)/DPVBi (8 nm)/DPVBi:DCJTB 0.5% (15 nm)/BPhen (x nm)/Alq₃ [(55−x) nm]/LiF (1 nm)/Al, with x=0, 4, and 7. BPhen was used as the hole-blocking layer. This results in a mixture of lights from DPVBi molecules (blue-light) and DCJTB (yellow-light) molecules, producing white light emission. The chromaticity can be readily adjusted by only varying the thickness of the BPhen layer. The CIE coordinates of the device are largely insensitive to the driving voltages. When the thickness of BPhen is 7 nm, the device exhibits peak efficiency of 6.87 cd/A (3.59 lm/W) at the applied voltage of 6 V, the maximum external quantum efficiency η_ext=2.07% corresponding to 6.18 cd/A, and the maximum brightness is 18494 cd/m² at 15 V.     

Blue organic light-emitting diodes with low driving voltage and maximum enhanced power efficiency based on buffer layer MoO3

Blue organic light-emitting devices based on wide bandgap host material, 2-(t-butyl)-9, 10-di-(2-naphthyl) anthracene (TBADN), blue fluorescent styrylamine dopant, p-bis(p-N,N-diphenyl-amino-styryl)benzene (DSA-Ph) have been realized by using molybdenum oxide (MoO₃) as a buffer layer and 4,7-diphenyl-1,10-phenanthroline (BPhen) as the ETL. The typical device structure used was glass substrate/ITO/MoO₃ (5 nm)/NPB (30 nm)/[TBADN: DSA-Ph (3 wt%)](35 nm)/BPhen (12 nm)/LiF (0.8 nm)/Al (100 nm). It was found that the MoO₃∥BPhen-based device shows the lowest driving voltage and highest power efficiency among the referenced devices. At the current density of 20 mA/cm², its driving voltage and power efficiency are 5.4 V and 4.7 Lm/W, respectively, which is independently reduced 46%, and improved 74% compared with those the m-MTDATA∥Alq₃ is based on, respectively. The J-V curves of ‘hole-only’ devices reveal that a small hole injection barrier between MoO₃∥NPB leads to a strong hole injection, resulting low driving voltage and high power efficiency. The results strongly indicate that carrier injection ability and balance shows a key significance in OLED performance.     

White organic light emitting diodes based on DCM dye sandwiched in 2-methyl-8-hydroxyquinolinolatolithium

Stable white electroluminescence (EL) has been achieved from organic LED, in which an ultrathin 4-(dicyanomethylene)-2-methyl-6-(p-dimethyl-aminostyryl)-4H-pyran (DCM) dye layer has been inserted in between two 2-methyl-8-hydroxyquinolinolatolithium [LiMeq] emitter layer and by optimizing the position of the DCM dye layer from the α-NPD/LiMeq interface. Electroluminescence spectra, current-voltage-luminescence (I-V-L) characteristics of the devices have been studied by changing the position of the dye layer. As the distance of DCM layer from α-NPD/LiMeq interface is increased, the intensity of host emission enhances rapidly. Introduction of thin layer of DCM in emissive layer increases the turn on voltage. The best Commission International de L’ Eclairage (CIE) coordinates i.e. (0.32, 0.33) were obtained with device structure ITO/α-NPD(30 nm) /LiMeq(10 nm)/DCM(1 nm)/LiMeq(25 nm)/BCP(6 nm)/Alq₃(28 nm)/LiF(1 nm)/Al(100 nm). The EL spectrum covers the whole visible spectra range 400-700 nm. The color rendering index (CRI) for our best white light (Device 4) is 47.4. The device shows very good color stability in terms of CIE coordinates with voltages. The maximum luminescence 1240 cd/m⁻² has been achieved at 19 V.     

Characterization of two-emitter WOLED with no additional blocking layer

In this paper, white organic light emitting diodes (WOLEDs) utilizing two primary-color emitters with no additional blocking layer are fabricated. With a structure of ITO/2TNATA (20 nm)/NPB (20 nm)/NPB: rubrene (2%) (10 nm)/ADN (30 nm)/Alq₃ (20 nm)/LiF (1 nm)/Al (100 nm), a white light with CIE coordinates of (0.344, 0.372) is generated at a current density of 30 mA/cm² and the electroluminescence (EL) spectra consist of two broad bands around 456 nm (ADN) and 556 nm (NPB:rubrene). The device shows the low turn-on voltage and bright white emission with a power efficiency of 2.3 lm/W at a luminance of 100 cd/m². Through control of the location of the recombination zone and energy transfer, a stable white light emission is achieved. The maximum color shift is less than 0.02 units on the 1931 CIE x,y chromaticity diagram. Given the spectral power distribution of WOLED, the parameters of a light source (chromaticity coordinate, CCT, CRI, and the luminous efficacy) can be calculated. A MATLAB program for this purpose is developed in this paper. Based on this, the design of WOLED for an illumination and display system using a white emitter with color filter arrays is discussed.     

Efficient and stable single-dopant white OLEDs based on 9,10-bis (2-naphthyl) anthracene

Efficient white organic light-emitting diodes (WOLEDs) are fabricated with a thin layer of 9,10-bis (2-naphthyl) anthracene (ADN) doped with Rubrene as the source of white emission. A device with the structure of ITO/NPB (70 nm)/ADN: 0.5% Rubrene (30 nm)/Alq₃ (50 nm)/MgAg shows a maximum current efficiency of 3.7 cd/A, with the CIE coordinates of x=0.33, y=0.43. The EL spectrum of the devices and the CIE coordinates remains almost the same when the voltage is increased from 10 to 15 V and the current efficiency remains quite stable with the current density increased from 20 to 250 mA/cm².     

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.     

Electrical conductivity and dynamics of quasi-solidified lithium-ion conducting ionic liquid at oxide particle surfaces

Lithium ion conducting solid-state composites consisting of lithium ion conducting ionic liquid, lithium bis(trifluoromethanesulfonyl)amide (Li-TFSA) dissolved 1-ethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)amide (EMI-TFSA), denoted by [yMLi⁺][EMI⁺][TFSA⁻] in this study, and various oxide particles such as SiO₂, Al₂O₃, TiO₂ (anatase and rutile) and 3YSZ are synthesized via a liquid route for the molar concentration of lithium, y, to be 1. The composite consists of SiO₂ and the ionic liquid with y = 0.2 was also prepared. The ionic liquid are quasi-solidified at the above oxide particle surfaces when x is below 40 for y = 1 and x is below 30 for y = 0.2, corresponding to the confinable thickness of the ionic liquid at the oxides' surfaces to be approximately 5-10 nm regardless of the oxide compositions. The electrical conductivities of x vol.%[yMLi⁺][EMI⁺][TFSA^-]-SiO₂, Al₂O₃, TiO₂s or 3YSZ composites are evaluated by ac impedance measurements. The quasi-solid-state composites exhibited liquid-like high apparent conductivity, e.g. 10^− 3.3-10^− 2.0 S cm^− 1 in the temperature range of 323-538 K for SiO₂-ionic liquid composites with y = 1. The self-diffusion coefficients of the constituent species of x vol.% [yMLi⁺][EMI⁺][TFSA⁻] (x is below 40, y = 0.2 and 1) − SiO₂ are evaluated by the Pulse Gradient Spin Echo (PGSE)-NMR technique in the temperature range of 298-348 K. By the quasi-solidification of the ionic liquid at SiO₂ particle surfaces, the absolute values of the diffusion coefficients of all constituent species decreased. The SiO₂ surfaces work to promote ionization of ion pair, [EMI⁺][TFSA⁻], while significant influence on the solvation coordination, [Li(TFSA)_n + 1]ⁿ⁻, was not observed. The apparent transport numbers of Li-containing species both in the bulk and the quasi-solidified ionic liquid showed similar values with each other, which was evaluated to be in the range of 0.010-0.017 for y = 0.2 and 0.051-0.093 for y = 1 in the abovementioned temperature range.     

Effect of nanoparticle size on magnetic damping parameter in Co92Zr8 soft magnetic films

Co₉₂Zr₈(50 nm)/Ag(x) soft magnetic films have been prepared on Si (111) substrates by oblique sputtering at 45°. Nanoparticle size of Co₉₂Zr₈ soft magnetic films can be tuned by thickening Ag buffer layer from 9 nm to 96 nm. The static and dynamic magnetic properties show great dependence on Ag buffer layer thickness. The coercivity and effective damping parameter of Co₉₂Zr₈ films increase with thickening Ag buffer layer. The intrinsic and extrinsic parts of damping were extracted from the effective damping parameter. For x=96 nm film, the extrinsic damping parameter is 0.028, which is significantly larger than 0.004 for x=9 nm film. The origin of the enhancement of extrinsic damping can be explained by increased inhomogeneity of anisotropy. Therefore, it is an effective method to tailor magnetic damping parameter of thin magnetic films, which is desirable for high frequency application.     

The effect of Pt on Ni3Al surface oxidation at low-pressures

The fully-oxidized surface that forms on (1 1 1) oriented Ni₃Al single crystals, with and without Pt addition, at 300-900 K under oxygen pressures of ca. 10⁻⁷ Torr was studied using XPS, AES, and LEIS. Two main types of surfaces form, depending upon oxidation temperature. At low-temperature, the predominant oxide is NiO, capped by a thin layer of aluminum oxide, which we refer to generically as Al_xO_y. At high-temperature (i.e., 700-800 K), NiO is replaced by a thick layer of Al_xO_y. By comparing samples that contain 0, 10 and 20 at.% Pt in the bulk, we find that the effect of Pt is to: (1) reduce the maximum amount of both NiO and Al_xO_y; and (2) shift the establishment of the thick Al_xO_y layer to lower temperatures. Platinum also decreases the adsorption probability of oxygen on the clean surface.     

NaCl/Ca/Al as an efficient cathode in organic light-emitting devices

An efficient cathode NaCl/Ca/Al used to improve the performance of organic light-emitting devices (OLEDs) was reported. Standard N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′ biphenyl 4,4′-dimaine (NPB)/tris-(8-hydroxyquinoline) aluminum (Alq₃) devices with NaCl/Ca/Al cathode showed dramatically enhanced electroluminescent (EL) efficiency. A power efficiency of 4.6 lm/W was obtained for OLEDs with 2 nm of NaCl and 10 nm of Ca, which is much higher than 2.0 lm/W, 3.1 lm/W, 2.1 lm/W and 3.6 lm/W in devices using, respectively, the LiF (1 nm)/Al, LiF (1 nm)/Ca (10 nm)/Al, Ca (10 nm)/Al and NaCl (2 nm)/Al cathodes. The investigation of the electron injection in electron-only devices indicates that the utilization of the NaCl/Ca/Al cathode substantially enhances the electron injection current, which in case of OLEDs leads to the improvement of the brightness and efficiency.     

Preparation of five-layered Si/SixGe1−x nano-films by RF helicon magnetron sputtering

Five-layered Si/Si_xGe_1−x films on Si(1 0 0) substrate with single-layer thickness of 30 nm, 10 nm and 5 nm, respectively were prepared by RF helicon magnetron sputtering with dual targets of Si and Ge to investigate the feasibility of an industrial fabrication method on multi-stacked superlattice structure for thin-film thermoelectric applications. The fine periodic structure is confirmed in the samples except for the case of 5 nm in single-layer thickness. Fine crystalline Si_xGe_1−x layer is obtained from 700 °C in substrate temperature, while higher than 700 °C is required for Si good layer. The composition ratio (x) in Si_xGe_1−x is varied depending on the applied power to Si and Ge targets. Typical power ratio to obtain x = 0.83 was 7:3, Hall coefficient, p-type carrier concentration, sheet carrier concentration and mobility measured for the sample composed of five layers of Si (10 nm)/Si_0.82Ge_0.18 (10 nm) are 2.55 × 10⁶ /°C, 2.56 × 10¹² cm⁻³, 1.28 × 10⁷ cm⁻², and 15.8 cm⁻²/(V s), respectively.     

A study of the properties and microstructure of Ni81Fe19 ultrathin films with MgO

The anisotropic magnetoresistance (AMR) of a Ta (5 nm)/MgO (3 nm)/Ni₈₁Fe₁₉ (10 nm)/MgO (2 nm)/Ta (3 nm) film with MgO-Nano Oxide Layer (NOL) increases dramatically from 1.05% to 3.24% compared with a Ta (5 nm)/Ni₈₁Fe₁₉ (10 nm)/Ta (3 nm) film without the MgO-NOL layer after annealing at 380 °C for 2 h. Although the MgO destroys the NiFe (1 1 1) texture, it enhances the specular electron scattering of the conduction electrons at the NOL interface and suppresses the interface reactions and diffusion at the Ta/NiFe and NiFe/Ta interfaces. The NiFe (1 1 1) texture was formed after the annealing, resulting in a higher AMR ratio. X-ray photoelectron spectroscope results show that Mg and Mg²⁺ were present in the MgO_x films.     

The effect of alkaline metal chlorides on the properties of organic light-emitting diodes

The multilayer organic light-emitting diodes (OLEDs) have been fabricated with a thin alkaline metal chloride layer inserted inside an electron transport layer (ETL), tris (8-hydroxyquinoline) aluminum (Alq₃). The alkaline metal chloride layer was inserted inside 60 nm Alq₃ at d=0, 10, 20 and 30 nm positions (d is the distance of the interlayer away from the Al cathode). The devices, with alkaline metal chlorides inserted at the Alq₃/Al interface, showed electron injection and electroluminescence (EL) intensity improvements. When the alkaline metal chlorides were inserted inside the Alq₃ layer at 10, 20 or 30 nm position apart from the Al cathode, both EL intensity and efficiency were enhanced for the devices with a thin potassium chloride (KCl) or rubidium chloride (RbCl) layer. On the contrary, the improvements were not observed for the OLEDs with a thin sodium chloride (NaCl) layer. A proposed insulator buffer layer model is employed to explain these characteristics of the devices.     

X-ray photoemission and X-ray absorption studies of Hf-silicate dielectric layers

Photoelectron spectroscopy and X-ray absorption spectroscopy (XAS) measurements have been performed on HfSi_xO_y and HfSi_xO_yN_z dielectric layers, which are potential candidates as high-k transistor gate dielectrics. The hafnium silicate layers, 3-4 nm thick, were formed by codepositing HfO₂ and SiO₂ (50%:50%) by MOCVD at 485 °C on a silicon substrate following an IMEC clean. Annealing the HfSi_xO_y layer in a nitrogen atmosphere at 1000 °C resulted in an increase in the Si⁴⁺ chemical shift from 3.5 to 3.9 eV with respect to the Si⁰ peak. Annealing the hafnium silicate layer in a NH₃ atmosphere at 800 °C resulted in the incorporation of 10% nitrogen and the decrease in the chemical shift between the Si⁴⁺ and the Si⁰ to 3.3 eV. The results suggest that the inclusion of nitrogen in the silicate layer restricts the tendency of the HfO₂ and the SiO₂ to segregate into separate phases during the annealing step. Synchrotron radiation valence band photoemission studies determined that the valence band offsets were of the order of 3 eV. X-ray absorption measurements show that the band gap of these layers is 4.6 eV and that the magnitude of the conduction band offset is as little as 0.5 eV.     

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.     

Ca1−xMo1−ySiyO4:Eux: A novel red phosphor for white light emitting diodes

Single phase of Ca_1−xMo_1−ySi_yO₄:Eu_x³⁺ (0.18?x?0.26, 0?y?0.04) was synthesized by solid-state method. The photoluminescence investigation indicated that Ca_1−xMoO₄:Eu_x³⁺ (0.18?x?0.26) could be effectively excited by 393 and 464 nm, and it exhibited an intense red emission at 615 nm. The introduction of Si⁴⁺ ions did not change the position of the peaks but strongly enhanced the emission intensity of Eu³⁺ under 393 and 464 nm excitations and showed very good color purity. The emission intensity of optimal Ca_0.8Mo_0.98Si_0.02O₄:Eu_0.2³⁺ sample (excited by 393 nm) was about 5.5 times higher than that of the phosphor Y₂O₂S:0.05Eu³⁺. So this phosphor could be nicely suitable for the application of the UV LED chips.     

FTIR and spectroscopic ellipsometry investigations of the electron beam evaporated silicon oxynitride thin films

FTIR and variable angle spectroscopic ellipsometer in conjunction with computer simulation were employed to investigate the electron beam evaporated SiO_xN_y thin films. FTIR showed a large absorption band located between 600 and 1250 cm⁻¹, which indicates that Si-O and Si-N bands are overlap in SiO_xN_y films. A three layers model was used to fit the calculated data to the experimental ellipsometric spectra. The main layer was described by Cauchy model while the interface layer and the surface layer were described using Tauc-Lorenz oscillator and Bruggeman effective medium approximation, respectively. The thickness, the refractive index and the extinction coefficient were accurately determined. The refractive index at 630 nm was found to increase from 1.74 to 1.85 with increasing the film thickness from 191.6 to 502.2 nm. The absorption coefficient was calculated from the obtained extinction coefficient values and it has been used to calculate the Tauc and Urbach energies.