In the past decades, polymeric light-emitting diode (PLED) have been a focus of research interest to scientists all over the world due to its potential application in flat panel displays. In previous studies, tremendous progresses in material developments, device engineering and theoretical modeling for PLEDs have been achieved. However, there are still a number of crucial problems to be solved in order for PLEDs to be widely employed in commercial flat panel displays. In this thesis, we present studies of PLEDs that used a high work-function metal aluminum as the cathode. The device exhibits a highly enhanced efficiency by modifying the cathode using certain non-ionic surfactant polymers. Based on this finding, we further demonstrated top-emitting PLEDs with environmentally stable cathodes. In another development, we show that a three-coloremitting device with a bilayer emitting polymer structure can be achieved by a dry photo-patterning process. Each of the red, green and blue emission in the device has a comparable emitting efficiency to the traditional standard red, green or blue device with single color emission. These results are believed to be important and beneficial for obtaining low-cost, large-scale and long life-time flat panel displays based on PLEDs. / by Deng Xianyu. / "September 2006." / Adviser: King Young Wong. / Source: Dissertation Abstracts International, Volume: 68-03, Section: B, page: 1871. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references (p. 92-101). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

Organic light-emitting diode (OLED) devices have been applied in the fields of display and solid-state lighting. In addition to phosphorescent OLEDs using heavy transition metals, a new approach of harvesting both singlet and triplet excitons generated in the OLED device by using pure organic materials has drawn a lot of attentions in recent years. It is thermally activated delayed fluorescence (TADF) process, which makes it possible to obtain potential 100% internal quantum efficiency (IQE);TADF is a process existing in certain organic materials with small singlet-triplet exchange energy (EST), which is generally observed in the molecules with weak-coupled electron-donating (D) group and electron-accepting (A) group. Individual molecule containing D/A, which is named intramolecular exciplex, or intermolecular exciplex with D/A on separated molecules, can fulfill this requirement. Although at present the intramolecular exciplex attracts considerable research interests, it takes a lot of efforts to design an individual molecule with high fluorescent quantum yield as well as small EST. Intermolecular exciplex, which is achieved by physically blending individual D and A molecules with appropriate selection from present materials, has excellent performance comparable to the phosphorescent emitter.;In this work, we studied the TADF process in an intermolecular exciplex and its application in highly efficient OLED devices. By doping electron-donating material tris(4-carbazoyl-9-ylphenyl)amine (TCTA) with electron-accepting material 2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine (Tm3PyBPZ), an exciplex with a green emission around 514 nm was demonstrated. The time-resolved photoluminescence of the exciplex under different temperatures from 12 K to 300 K demonstrated the existence of temperature-dependent delayed fluorescence. By applying this exciplex as the emissive layer, a highly efficient all-fluorescent organic lighting emitting diode with maximum efficiencies of 13.1% and 53.4 lm/W was realized with an extremely low turn-on voltage of only 2.4 V. The efficiencies of the device have outperformed conventional fluorescent OLED devices due to the contribution of triplet excitons. By doping this exciplex with other conventional green or yellow fluorescent dopants, we observed that the performances of these dopants also surpass the limitation of conventional fluorescent OLED (5̃ % external quantum efficiency)

Dramatic increase of energy consumption and environmental problems invigorate the development of organic semi-conductive materials to substitute for the conventional inorganic materials in the application of photovoltaic and light-emitting devices. In view of the merits of low driving voltage, high power conversion efficiency, large-area fabrication of thin and light organic films as well as saturated emission, organic light-emitting diodes (OLEDs) have received much more consideration by scientists in the past two decades. And even out of laboratory, the OLEDs are popular among the commercial electronic products for solid-state displays and illumination. Generally, three primary RGB emitters, involving red (R), green (G) and blue (B), are footstones to achieve solid-state displays and illumination because the spectra by compositing RGB emissions match very well with the solar spectrum. Also, the combination of two complementary luminophors, blue and orange or yellow is an alternative approach to simulate the solar spectrum for white light illumination. Except for the full-color light-emitting materials for solid-state displays and illumination, near infrared (NIR) organics are of great importance for applications in information-secured devices, communications, biosensors, and phototherapy. To date, uncountable research works focusing on the emitters for full-color emissions have demonstrated their synthesis, photophysical properties and OLED application, which shows enough efficiency and stability to commercial utility. However, there are still three challenging issues which are needed to be handled urgently. Firstly, the lack of efficient deep blue emitters makes the external quantum efficiency (EQE) of deep blue OLEDs around 10% when the Commission Internationale de l'Éclairage (CIE) coordinates of y is smaller than 0.1. On the one hand it is difficult to achieve the deep blue emitters with extremely broad energy gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). On the other hand the triplet and frontier energy levels of the host, electron transporting layer (ETL) and hole transporting layer (HTL) in the device are required to well match with that of the emitters. Secondly, high energy in the emissive layer (EML) of deep blue OLEDs may degrade the materials used inside the EML, resulting in their short lifetimes. Thirdly, by comparison with other colors, the investigations of NIR emitters, such as their preparation, property study and device fabrications are sparse.;By harvesting both 25% singlet and 75% triplet excited states, iridium(III) [Ir(III)] complexes have been proven to be one of the best candidates to achieve highly efficient phosphorescent OLEDs (PHOLEDs) for solid-state displays and illumination. Herein, based on Ir(III) complexes, 18 phosphors were synthesized to achieve a widely tunable phosphorescence from deep blue to NIR. In this thesis, their synthesis were fully characterized by NMR spectroscopy, mass spectrometry and X-ray crystallography. Further investigations on the photophysical, electrochemical and thermal properties reveal that these phosphors have the possibility of device fabrication. And rational design of device architectures afford the OLEDs with high efficiencies.;Firstly, N-heterocyclic carbene ligands (CˆC:) were used to elevate the LUMO of phosphors (Ir1-Ir7), resulting in true and deep blue emission spanning from 420 to 450 nm. Secondly, the widely tunable phosphorescence from 470 to 614 nm was accomplished by using polyfluorinated 2-phenylpyridine (CˆN) derivatives as cyclometallated ligands of Ir(III) complexes (Ir10-Ir17). Interestingly, electron-withdrawing trifluoromethyl (CF3) group on the phenyl ring of CˆN-type ligands results in significantly red-shifted emissions of Ir(III) complexes, which distinguishes with the blue-shift effect of fluoride approach. Lastly, by comparison with the reported literature on NIR Ir(III) phosphors with extensive conjugation, the addition of slight conjugation but electron-withdrawing moieties onto the pyridyl ligands is a powerful and convenient avenue to tune the phosphorescence of Ir(III) phosphor into the NIR region, emitting at 729 nm.;Meanwhile, the deepest blue OLED made from Ir1 showed a peak EQE of 7.1% with CIE of (0.16, 0.11). And the best deep blue OLEDs made from Ir7 by using single and double electroluminescent (EL) units gave the highest EQE of 19.0% and 31.5% with CIE coordinates of (0.15, 0.19) and (0.15, 0.22), respectively. Such high efficiencies are comparable to and even better than the currently reported deep blue PHOLEDs. Also, the sky blue, green, yellow, orange, red and NIR PHOLEDs fabricated from Ir10, Ir13, Ir15, Ir16, Ir17 and Ir18 afforded the maximum EQE of 11.2%, 20.1%, 15.4%, 9.9%, 6.8% and 4.0%, respectively. By stacking RGB EML, the white PHOLED (PHWOLED) made by Ir1, Ir13 and Ir17 gave a peak EQE of 16.0% and CIE of (0.36, 0.47).;All in all, this thesis has successfully combined the materials synthesis and devices design to achieve efficient full-color and NIR PHOLEDs which are of great interest for solid-state displays and illumination. These works have a great significance in terms of the improvement of efficiency and stability of deep blue OLEDs as well as simplifying the synthesis methods to prepare highly efficient NIR Ir(III) phosphors.

The structural design, synthesis and characterization of luminogens with aggregation-induced emission (AIE) properties are studied in this thesis. The remarkable emission properties, thermal stability and biocompatibility of the AIE-active materials demonstrate the promising applications in bioimaging and organic light-emitting diodes (OLEDs).;Chapter 1 introduces the existence of aggregation-caused quenching (ACQ) effect in most conventional organic dyes as well as phosphorescent transitional metal complexes. Discovery of AIE and its mechanical study allow further exploration of usage in organic luminescent materials. This chapter also gives some examples and the applications these AIE-active compounds.;In Chapter 2, a series of cyanostilbenes with simple electron donor (D)-p-electron acceptor (A) structure are presented and synthesized. They exhibit remarkable AIE effect as well as deep red emission peak in 95 % water fraction in THF. These results indicate that attachment of these electron acceptors provides alternative strategy for designing highly emissive AIE-active materials.;In Chapter 3, strongly emissive cyanostilbenes with phenothiazine unit are designed and synthesized. This chapter also investigates the effect of substituents in phenothiazine and terminal cyanostilbene on the photophysical properties and AIE effect. The results suggest that they are AIE-active with different sizes in nano-aggregates. Furthermore, these dyes exhibit clear and strong fluorescence in live cell imaging with excellent biocompatibility.;In Chapter 4, a series of AIE-active phosphorescent Pt(II) complexes made up of C^N^C tridentate ligands are designed and synthesized. They exhibit different morphologies and emission properties upon aggregation in 90 % water in acetonitrile although similar tridentate ligands are applied. One of the complexes in this chapter show nano-rod formation with the highest quantum efficiency in aggregated state, suggesting that rapid self-assembly process occurs to prevent non-radiative decay and oxygen quenching.;In Chapter 5, a series of bis-cyanostyryl fluorophores are designed and synthesized. They are emissive in solid state with colour range from orange to NIR region. Furthermore, they are AIE-active and some of them may contain hybridized local and charge transfer (HLCT) excited state to achieve highly efficient emission upon solvatochromic investigation. Some bis-cyanostyryl thiophenes are fabricated in OLED devices show deep-red to NIR emission, indicative of a promising way to design solid-state NIR-emissive compounds using bis-cyanostyryl derivatives.;Finally, Chapter 6 and 7 present the concluding remarks and the experimental details of the work in Chapters 2 to 5, respectively.

published_or_final_version / Electrical and Electronic Engineering / Master / Master of Philosophy

The plasmonic properties of silver-based alloy thin films were studied. Silver-ytterbium (Ag-Yb) and silver-magnesium (Ag-Mg) prepared by thermal co-evaporation were investigated extensively for various thin film properties. The optical properties were intensively analyzed and discussed because the dielectric response of a material is particularly significant in terms of its plasmonic properties. The study of silver-based alloy thin films has been mostly about Ag alloying with other transition metals, but the results of Ag-Yb and Ag-Mg in this work showed that the intensity of plasma resonance is tunable, in which the idea may also apply to other silver-rich binary alloy thin films regardless of the kind of second metal components. In our research, the Ag plasma resonance was weakened with respect to the concentration of Yb and Mg in the alloy thin films. The change in the optical characteristics around Ag plasma resonance frequency was attributed to an increase in “resonance damping. This is confirmed from modeling using classical free-electron theory. The increase in the damping was experimentally corroborated by the concentration dependence of electrical conductivity and estimated average crystallite size of Ag-Yb and Ag-Mg thin films. The reduction in electrical conductivity was not only caused by introducing less conductive Yb or Mg but also through disturbing the Ag lattice structure to promote additional electron scattering at grain boundaries. The Ag-Yb and Ag-Mg alloys carried intermediate properties between their pure components despite the presence of Yb or Mg oxides. Besides optical and electrical properties, changes in the electronic work function were also assessed since it is also important in applications. Plasmonic nanostructures and transparent organic light-emitting diodes (OLEDs) were fabricated to demonstrate their potential applications. Two-dimensional disc-arrays nanostructures composed of pure Ag and Ag-Yb were implemented to evaluate the plasmonic properties. The damping loss in Ag-Yb caused weakened coupling of incident photons and surface plasmons when compared to pure Ag without altering the coupling wavelengths, suggesting potential plasmonic materials for tuning the coupling strength of surface plasmons by controlling the concentration of Yb which may also apply to Ag-Mg. Ultrathin Ag-Yb and Ag-Mg films were used as cathodes in transparent OLEDs for demonstration, which was beneficial by virtue of overall device transmittance though sacrificing electrical conduction leading to poor light emission unless inserting additional ultrathin lithium fluoride to modify the ultrathin cathodes.

Organic light-emitting diodes (OLEDs) have been considered as the future lighting and display system and rapidly growing since 1987. It has been already used in many commercial applications such as OLED televisions, cell phone displays, and lighting systems. The OLED has higher luminous efficiency and extremely thinner layer compare to any other lighting devices, also it has flexibility and self-emission. However, there are still some drawbacks for the device performances such as lifetime especially on blue organic films, cost of manufacturing process, and moisture that we need to work on before wide-scale commercialization like LCD or LED. This thesis has focused on developing a charge distribution such as deriving empirical equations in multi-emissive layer OLED, improving external quantum efficiency (EQE) and lowering roll-off. Key results are summarized as follows: (1)We seek to establish a quantitative method to estimate the holes and electrons ratio in the recombination zones. The result shows a trend in the charge recombination ratio depending on the hole and electron transport layer (HTL/ETL) thickness. We obtained an empirical relationship between electron/hole transport layer thicknesses and emission ratio in emissive layer (EML). In addition, the electroluminescence (EL) spectra were analyzed by fitting a Gaussian distribution for the two emissive layers to calculate the intensity ratio of the energy transitions. The arrival time of hole and electrons from each electrode was determined using the thickness and mobility of NPB as hole transport layer and TPBi as electron transport layer. From these initial results, we derived an empirical mechanism to meet with an exponential relationship that can allow us to design custom- made OLEDs. (2)We fabricated White OLEDs in which the emissive layers are chemically doped with blue and red fluorescent dopants of BUBD-1 and DCJTB. This work continues by estimating of emission ratio between red and blue emissive layers by changing the thicknesses of HTL and ETL. The recombination of charge carriers was first identified the location and then we derived an empirical equation for peak intensity ratio of EL spectra with respect to thickness of the HTL/ETL to determine how recombination zone depends on the HTL and ETL thickness. The EL spectra of WOLEDs were fitted with a Gaussian distribution for the two emissive layers using host-dopant system and intensity ratio of blue and red emission peak is 61:39 when thickness of HTL and ETL are 80nm and 20nm, respectively. Also, this intensity ratio of blue and red emission peak (61:39) has the CIE color coordinates of (0.34, 0.40). We obtained a preliminary relationship between thickness of electron/hole transport layer and ratio of two emission peaks. (3)The improved external quantum efficiency (EQE) and reduced roll-off properties of blue phosphorescent organic light-emitting diodes (PHOLEDs), were obtained with structure, ITO/NPB (40 nm)/TCTA (20 nm)/mCP:FIrpic (7%)(30 nm)/TPBi (30 nm)/Liq (2 nm)/Al (80 nm) by incorporating a TCTA inter-layer. We compared the properties of BCP and TPBi as the ETL with a typical structure of HTL/ EML/ETL in OLEDs and utilized inter-layer in the optimized structure to enhance EQE to 52% at 5.5 V, also stabilize the roll-off of 63%. The use of inter-layer in blue PHOLEDs exhibits a current efficiency of 10.04 cd/A, an EQE of 6.20% at 5.5 V and the highest luminance of 10310 cd/m2 at 9.5 V.