Luminescence properties of poly(9,9-dioctylfluorene)/polyvinylcarbazole blends: Role of composition on the emission colour stability and electroluminescence efficiency

Light-emitting diodes (LEDs), based on blue-emitting polyfluorenes are usually prone to the appearance of a contaminant green emission (centered around 520 nm), leading to an apparent whitish light emission. We find that, for LEDs based on poly(9,9-dioctylfluorene), PFO, the blending with the hole transporting polyvinylcarbazole, PVK, can suppress such green emission. LEDs based on a PFO/PVK blend with a 1:2 weight ratio and with aluminum cathodes show a quite stable blue emission. This result reveals the important role played by the interchain interactions on the observed contaminant green emission. In addition, we observe that in Al-based devices blending causes a decrease in EL efficiency while in Mg-based devices we obtained higher efficiencies with the blend PFO:3PVK when compared with neat PFO-based devices.     

有机薄膜晶体管驱动聚合物发光二极管研究

研究了有机薄膜晶体管(OTFT)与聚合物发光二极管(PLED)集成制备技术和相关物理问题.OTFT结构为栅极钽(Ta)/绝缘层五氧化二钽(Ta2O5)/有源层并五苯(Pentacene)/源漏极金(Au);PLED器件结构为ITO/PEDOT:PEO(polyethylene oxide)/P-PPV或MEH-PPV/Ba/Al.PEDOT:PEO,P-PPV和MEH-PPV薄膜层均采用丝网印刷技术,实现了OTFT与PLED器件集成发光.其中OTFT器件的阈值电压为-7V,迁移率为0.91cm2/(V.s),并通过OTFT驱动得到以P-PPV和MEH-PPV为发光层的PLED器件的发光亮度分别达到124和26cd/m2,电流效率分别为12.4和1.1cd/A.利用丝网印刷技术可以有效控制高分子薄膜的沉积区域,实现功能器件的集成.     

高效率共轭聚合物主体绿光磷光发光二极管

因电致发光效率高和器件制备工艺简单,聚合物为主体的绿色磷光电致发光成为一个研究热点.共轭聚合物的三线态能级一般低于绿色磷光材料的三线态能级,易对磷光的发光引起猝灭导致低的发光效率,所以较少被用作绿色磷光材料的主体.通过增加聚乙烯基咔唑（PVK）作为空穴传输层,获得了高发光效率的共轭聚合物聚芴（PFO）作主体绿色磷光发射,甚至高于相同条件下以PVK为主体的绿色磷光发射.究其原因,PVK的电子阻挡作用使发光中心靠近PVK与PFO的界面,界面处PVK因为其高的三线态能级增强了绿色磷光的发光.当三-（2-苯基吡啶）-Ir（Ir（ppy）₃）掺杂浓度为2％时得到了最高的亮度效率24.8 cd/A,此时的电流密度为4.65 mA/cm²,功率效率为11 lm/W,最高亮度达到35054 cd/m²,色坐标是（0.39,0.56）. 关键词： 共轭聚合物 磷光 绿光发光     

Polymer White-Light-Emitting Diodes with High Work Function Cathode Based on a Novel Phosphorescent Chelating Copolymer

Polymer white-light-emitting diodes are fabricated based on the blend of poly[9,9-di-（2-ethylhexyl）-fluorenyl-2, 7- diyl]-end capped with polysilsesquioxane （PFO） and a chelating copolymer of poly[（9,9-bis（3′-（N,N-dimethylamino） propyl）-2, 7-fluorene-alt-2, 7-（9,9-dioctylfluorene） ）-co- [2, 7-（9,9-dioctlyfluorene）-alt-5,5-bis（2-（4-methyl-l-naphtha- lene） pyridine-C^2,N） iridium （III） acethylacetonate]] （PFN-NaIr）. The device with the sole aluminium cathode is able to produce a comparably white electroluminescence efficiency of 1.31 cd/A to that of the device using low work function cathodes （such as Ba, Ca, etc.）. The CIE coordinates of the white light emission consisting of red, green and blue three components are nearly at （0.34, 0.35）. The mechanism of the white light emission from the device with the AI cathode is investigated, which is related to the efficient injection of electrons through the interface of PFN-Nalr/AI.     

Study of temperature dependence and angular distribution of poly(9,9-dioctylfluorene) polymer films deposited by matrix-assisted pulsed laser evaporation (MAPLE)

Poly(9,9-dioctylfluorene) (PFO) polymer films were deposited by matrix-assisted pulsed laser evaporation (MAPLE) technique. The polymer was diluted (0.5 wt%) in tetrahydrofuran and, once cooled to liquid nitrogen temperature, it was irradiated with a KrF excimer laser. 10,000 laser pulses were used to deposit PFO films on 〈1 0 0〉 Si substrates at different temperatures (−16, 30, 50 and 70 °C). One PFO film was deposited with 16,000 laser pulses at a substrate temperature of 50 °C. The morphology, optical and structural properties of the films were investigated by SEM, AFM, PL and FTIR spectroscopy. SEM inspection showed different characteristic features on the film surface, like deflated balloons, droplets and entangled polymer filaments. The roughness of the films was, at least partially, controlled by substrate heating, which however had the effect to reduce the deposition rate. The increase of the laser pulse number modified the target composition and increased the surface roughness. The angular distribution of the material ejected from the target confirmed the forward ejection of the target material. PFO films presented negligible modification of the chemical structure respect to the bulk material.     

Enhanced Green Electrophosphorescence from Oxadiazole-Functionalized Iridium Complex-Doped Devices Using Poly（9,9-Dioctylfluorene） Instead of Poly（N-Vinylcarbazole） as a Host Matrix

Optoelectronic properties of the oxadiazole-functionalized iridium complex-doped polymer light-emitting devices （PLEDs） are demonstrated with two different polymeric host matrices at the dopant concentrations 1-8%. The devices using a blend of poly（9,9-dioctylttuorene）（PFO） and 2-（4-biphenyl）-5-（4-tert-butylphenyl）-1,3,4-oxadiazole （PBD） as a host matrix exhibited a maximum luminance efficiency of 11.3 cd/A at 17. 6 mA/cm^2. In contrast, the devices using a blend of poly（N-vinylcarbazole） （PVK） and PBD as a host matrix reveal only a peak luminance efficiency of 6.Scd/A at 4.1 mA/cm^2. The significantly enhanced electrophosphorescent emissions are observed in the devices with the PFO-PBD blend as a host matrix. This indicates that choice of polymers in the host matrices is crucial to achieve highly efficient phosphorescent dye-doped PLEDs.     

Efficient green-phosphorescent light-emitting diodes based on polymeric binary-host systems

The fabrication of the green polymer light-emitting diodes based on emission from the phosphorescent molecule fac tris(2-phenylpyridine) iridium doped into a polymeric binary-host is reported. The main host used in the PLEDs was a non-conjugated polymer, poly(9-vinyl carbazole) (PVK). To realize the balanced transport of the holes and the electrons, a conjugated polymer, poly(9,9-dioctylfluorene) (PFO) was used as the assisting host. According to the experimental results, we found that the PLEDs can achieve the balance in charge transport and the recombination zone is still confined in the emissive layer by controlling the ratio of PVK to PFO. The luminous efficiency is enhanced by >40% while the external quantum efficiency can be increased by >38% in a polymeric binary-host system as compared to those of traditional device configuration, which is attributed to the balanced transport of the charged carrier.     

Enhancing the performance of polymer light-emitting diode via methanol treatment

Enhanced performance of polymer light-emitting diodes (PLEDs) was realized by performing methanol treatment on the emissive layer. Experimental results show that with methanol treatment the electron current increased owing to the rougher surface topography of the emissive layer. Therefore, the balance between electron and hole current was improved. The maximum luminous efficiency and external quantum efficiency of PLEDs increased from 19.7 cd/A and 6.89% to 22.5 cd/A and 7.87%, respectively.     

Efficient Top-Emitting Polymer Light-Emitting Diodes Using Chromium as Anode

We demonstrate a high eftlciency top-emitting polymer light-emitting diode （TPLED） with chromium （Cr） taking as the anode. The TPLED structure is Cr/poly-3, 4-ethylenedioxythiophene （PEDOT：PSS）/poly [2-（4-3＇,7＇- dimethyloctyloxy）-phenyl]-p-phenylenevinylene） （P-PP V） /Ba/Ag. The Cr （ 100 nm） anode is prepared by sputterdepositing in a vacuum chamber. It is found that the device emissive properties are affected dramatically by the thickness of both PEDOT：PSS and the Ag cathode. Optimized thicknesses of PEDOT：PSS and Ag layer are 60nm and 15nm, respectively. The diode exhibits excellent electroluminescence （EL） properties, such as a turn-on voltage of 3.32 V, luminous eftlciency of 4.41 cd/A and luminance of 6989cd/m^2 at driving voltage of about 9 V.     

Effect of the polymer emission on the electroluminescence characteristics of n-ZnO nanorods/p-polymer hybrid light emitting diode

Hybrid light emitting diodes (LEDs) based on zinc oxide (ZnO) nanorods and polymers (single and blended) were fabricated and characterized. The ZnO nanorods were grown by the chemical bath deposition method at 50°C. Three different LEDs, with blue emitting, orange-red emitting or their blended polymer together with ZnO nanorods, were fabricated and studied. The current–voltage characteristics show good diode behavior with an ideality factor in the range of 2.1 to 2.27 for all three devices. The electroluminescence spectrum (EL) of the blended device has an emission range from 450 nm to 750 nm, due to the intermixing of the blue emission generated by poly(9,9-dioctylfluorene) denoted as PFO with orange-red emission produced by poly(2-methoxy-5(20-ethyl-hexyloxy)-1,4-phenylenevinylene) 1,4-phenylenevinylene) symbolized as MEH PPV combined with the deep-band emission (DBE) of the ZnO nanorods, i.e. it covers the whole visible region and is manifested as white light. The CIE color coordinates showed bluish, orange-red and white emission from the PFO, MEH PPV and blended LEDs with ZnO nanorods, respectively. These results indicate that the choice of the polymer with proper concentration is critical to the emitted color in ZnO nanorods/p-organic polymer LEDs and careful design should be considered to obtain intrinsic white light sources.     

Increased luminance of MEH-PPV and PFO based PLEDs by using salmon DNA as an electron blocking layer

The effect of salmon DNA-CTMA as an electron blocking layer (EBL) has been examined on the performance of MEH-PPV and PFO-based light emitting diodes. Though the turn-on voltage increases with incorporation of EBL, a significant increase in luminance and luminous efficiency for both the devices is observed. The EBL improves the device performance by blocking electrons at the EBL-polymer interface, thereby increasing the recombination probability of electrons and holes. The luminance of the MEH-PPV based Bio-LED increases to 100 cd/m² from 30 cd/m² while a corresponding increase for the PFO based LED is to 160 cd/m² from 80 cd/m² with and without EBL, respectively.     

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.     

Efficient small molecular and polymer organic devices using bis[2-(4-tert-butylphenyl)benzothiazolato-N,C′] iridium (III) (acetylacetonate) dye as emitter

Small molecular organic light-emitting diodes (MOLED) and polymer organic light-emitting diodes (POLED) were fabricated with yellow light emission phosphorescent dye bis[2-(4-tert-butylphenyl)benzothiazolato-N,C²′] iridium (III) (acetylacetonate) doped in different hosts. The electroluminescent (EL) spectra of both devices shown two peaks generated from iridium dye but the position of main peak changed and became broader for POLED. The maximum luminance of 10,500 cd/m² achieved at 12.5 V for MOLED is higher than maximum luminance of 9996 cd/m² at 20 V for POLED. The maximum power efficiency of small molecular device is 6.4 lm/W, which is higher than 2.3 lm/W of polymer device, but the efficiency of both devices will roll off at large current density.     

The effects of photochemical oxidation and chain conformation on green emission of poly(9,9-dioctylfluorene)

The effects of chain conformation on the photo-oxidation and green emission of poly(9,9-dioctylfluorenyl-2,7-diyl) (PFO) has been investigated at both single-molecule and ensemble levels. Single-molecule studies reveal the conformation of PFO chains to be more globular when cast from THF than from toluene solutions. Intensity transients of the single molecules show that the elongated molecules cast from toluene have more fluctuations due to limited energy transfer along the polymer chains. The more globular chains show monotonic decays with isotropic polarization. Emission spectra of the single molecules show that photochemical oxidation leads to a reduction in the emission of the molecule with no change in the emission spectra. No green emission is ever detected for single molecules, indicating that formation of emissive ketone defects is a rare event. Ensemble studies of chains show that molecules cast from THF develop some green emission upon photodegradation, while those cast from toluene do not. The increase in green emission in the globular molecules suggests that interchain contacts improve energy transfer for emissive ketone defects in the PFO cast from THF.     

Enhanced luminance of white organic light-emitting diode with yellow nanophosphors-embedded blue polymer emitting layer

White organic light-emitting device was achieved through an incorporation of yellow YAG nanophosphors into blue polyfluorene emitting layer: electrode/YAG@polyfluorene/hole-transport/injection layers/ITO glass. The brightness of the proposed device (230 cd/m² at 30 V) was enhanced by a factor of about two in comparison with that of phosphor-free reference device. It is attributed to the increased local electric field caused by bumps of nanophophors on the emitting layer. With increase of voltage, the blue-green emission decreased whereas the yellow emission increased. It is due to the effective energy transfer from the blue-green to the yellow bands.     

Enhanced field emission and patterned emitter device fabrication of metal-tetracyanoquinodimethane nanowires array

Ag(TCNQ) and Cu(TCNQ) nanowires were synthesized via vapor-transport reaction method at a low temperature of 100 °C. Field emission properties of the as-obtained nanowires on ITO glass substrates were studied. The turn-on electric fields of Ag(TCNQ) and Cu(TCNQ) nanowires were 9.7 and 7.6 V/μm (with emission current of 10 μA/cm²), respectively. The turn-on electric fields of Ag(TCNQ) and Cu(TCNQ) nanowires decreased to 6 and 2.2 V/μm, and the emission current densities increased by two orders at a field of 8 V/μm with a homogeneous-like metal (e.g. Cu for Cu(TCNQ)) buffer layer to the substrate. The improved field emission is due to the better conduct in the nanowires/substrate interface and higher internal conductance of the nanowires. The patterned field emission cathode was then fabricated by localized growing M-TCNQ nanowires onto mask-deposited metal film buffer layer. The emission luminance was measured to be 810 cd/m² at a field of 8.5 V/μm.     

修饰阴极界面提高聚合物白光二极管发光效率

利用聚合物的不同溶解性,研究用旋涂方法制备双层高分子白光二极管(WPLED),采用器件结构为：ITO/PEDOT(50nm)/PVK:PFO-BT: PFO-DBT(40nm)/PFO(40nm)/Ba(4nm) /Al(120nm),当相对比例为PVK: PFO-BT:PFO-DBT=1∶4%：3%时,得到标准白光,最大电流效率为2.4 cd/A,最大亮度为3215 cd/m²,色坐标为(0.33,0.34).用水溶性的聚电介质层修饰阴极界面,器件效率可以进一步提高到5.28 cd 关键词： 聚合物发光二极管 白光 双发光层结构     

Enhanced quantum efficiency in polymer electroluminescence devices by inserting an ultrathin PMMA layer

We report an increase of electroluminescence (EL) efficiency by about two times for poly(2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylene vinylene) (MEH-PPV) based polymer light-emitting diodes (PLED) while employing an ultrathin layer of poly(methyl methacrylate) (PMMA) between a hole injection layer, polyethylenedioxythiophenne:polystyrenesulfonate (PEDOT:PSS) and an emitting layer, MEH-PPV. The peak power efficiency of the control device (ITO/MEH-PPV/LiF/Al) was 0.42 lm/W with a current efficiency of 0.66 cd/A. The device with the optimized thickness of PMMA interface layer shows the highest power efficiency of 1.15 lm/W at a current efficiency exceeding 1.83 cd/A. The significant improvement in the device performance is attributed to the decrease of holes injection and the promotion of electrons injection, which cause the balance of the carriers within the emitting layer.     

A comparative study of electrode effects on the electrical and luminescent characteristics of Alq3/TPD OLED: Improvements due to conductive polymer (PEDOT) anode

The performance of organic light emitting device (OLED) structures, based on identically fabricated Alq₃/TPD active regions, with various anode and cathode electrode structures are compared, and performance differences related to the different anode structure. The best performance was achieved with a conductive polymer, 3,4-polyethylenedioxythiopene-polystyrenesultonate (PEDOT), used as an anode layer, yielding a brightness of 1720 cd/m² at 25 V, a turn-on voltage of 3 V, and electroluminescence (EL) efficiency and external quantum efficiency of 8.2 cd/A and 2%, respectively, at a brightness of 100 cd/m² and 5 V. Compared to a baseline device (TPD/Alq₃/Al), PEDOT anodes substantially reduce the turn-on voltage and made current injection almost linear after turn-on, whiles devices incorporating a LiF and CuPc layers significantly improved device efficiency while slightly improving turn-on voltage and maintaining superlinear I-V injection. This is attributed to the reduced barrier at the organic-organic interface in PEDOT, the ‘ladder’ effect of stepping the band offset over several interfaces, and the favorable PEDOT film morphology. The benefit of the PEDOT anode is clearly seen in the improvement in device brightness and the high external quantum efficiency obtained.     

Characterization of the hole transport and electrical properties in poly(9,9-dioctylfluorene)

A systematic study of the hole transport and electrical properties in blue-emitting polymers as poly(9,9-dioctylfluorene) (PFO) has been performed. We show that the temperature dependent and thickness dependent current density versus voltage characteristics of PFO hole-only devices can be accurately described using our recently introduced improved mobility model based on both the Arrhenius temperature dependence and non-Arrhenius temperature dependence. Within the improved model, the mobility depends on three important physical quantities: temperature, carrier density, and electric field. For the polymer studied, we find the width of the density of states σ=0.115 eV and the lattice constant a=1.2 nm. Furthermore, we show that the boundary carrier density has an important effect on the current density versus voltage characteristics. Too large or too small values of the boundary carrier density lead to incorrect current density versus voltage characteristics. The numerically calculated carrier density is a decreasing function of distance from the interface. The numerically calculated electric field is an increasing function of distance. Both the maximum of carrier density and minimum of electric field appear near the interface.