The use of polymers in electro-optical devices, especially light-emitting diodes (OLEDs), has become very popular in recent years, due to their ease of processability. The major drawback of using polymers in these systems is their time-consuming synthesis when trying to improve upon their physical properties. For example, each time a new color or better conducting properties are desired, a new monomer must be synthesized. To circumvent these problems, the system described in this work is designed to connect the well-known chromophore aluminum tris(8-hydroxyquinoline) (Alq3) to a norbornene monomer unit, followed by polymerization using ring-opening metathesis polymerization (ROMP), thus allowing for the processability of a polymer while maintaining the fluorescent properties of the metalloquinolate. The benefit of this system is that the monomers can be easily altered in order to tune color emission or to enhance the polymer properties. Some of the alterations include changing the metal center from aluminum to zinc in order to improve electron injection, adding substituents to the 8-hydroxyquinoline ligand in order to tune the emission color, and copolymerizing the Alq3-monomer with other norbornene monomers containing either a hole- or an electron-transport material side-chain to improve conductivity. These alterations lead to improved device performance and, more importantly, to a new method of designing polymeric systems for use in electronic devices.

Compared with its inorganic counterpart, organic thin-film transistor (OTFT) has advantages such as low-temperature fabrication, adaptability to large-area flexible substrate, and low cost. However, they usually need high operating voltage and thus are not suitable for portable applications. Although reducing their gate–dielectric thickness can lower the operating voltage, it increases their gate leakage. A better way is making use of high-κ gate dielectric, which is the main theme of this research. Firstly, pentacene OTFTs with HfO2 gate dielectric nitrided in N2O or NH3 at 200 oC were studied. The NH3-annealed OTFT displayed higher carrier mobility, larger on/off current ratio, smaller sub-threshold swing and smaller Hooge?s parameter than the N2O-annealed device. All these advantages were attributed to more nitrogen incorporation at the dielectric surface by the NH3 annealing which provided stronger passivation of surface traps. The incorporation of lanthanum to hafnium oxide was demonstrated to realize enhanced interface in the pentacene OTFTs. Therefore, pentacene OTFTs with HfLaO gate dielectric annealed in N2, NH3, O2 or NO at 400 oC were investigated. Among the 4 devices, the NH3-annealed OTFT obtained the highest carrier mobility, smallest sub-threshold swing and smallest 1/f noise. All these should be attributed to the improved interface between the gate dielectric and the organic semiconductor associated with the passivation effects of the NH3 annealing on the dielectric surface. The processing temperature of OTFTs is a big concern because use of flexible or glass substrate is the trend in organic electronics. Therefore, the HfLaO gate dielectric was annealed in N2, NH3, or O2 at two different temperatures, 200 oC and 400 oC. For all the annealing gases, the OTFTs annealed at 400 oC achieved higher carrier mobility, which could be supported by SEM image that pentacene tended to form larger grains (thus less carrier scattering) on HfLaO annealed at 400 oC. Furthermore, the HfLaO film annealed at 400 oC achieved much smaller leakage because more thermal energy at higher annealing temperature could remove oxide defects more effectively. Fluorination of the HfLaO film (annealed in N2 or NH3 at 400 oC) in a plasma based on CHF3 and O2 was also proposed. For both annealing gases, the OTFT with a 100-s plasma treatment achieved higher carrier mobility and smaller 1/f noise than that without plasma treatment. All these improvements should be due to fluorine incorporation at the dielectric surface which passivated the traps there. By contrast, for longer time (300 s or 900 s) of plasma treatment, the performance of the OTFTs deteriorated due to damage of dielectric surface induced by excessive plasma treatment. Lastly, a comparative study was done on pentacene OTFTs with HfLaO or La2O3 as gate dielectric. For the same annealing gas (H2, N2, NH3, or O2 at 400 oC), the OTFT with La2O3 gate dielectric obtained lower carrier mobility, smaller on/off current ratio, and larger threshold voltage than that based on HfLaO. The worse performance of the OTFTs with La2O3 gate dielectric was due to the degradation of La2O3 film caused by moisture absorption. / published_or_final_version / Electrical and Electronic Engineering / Doctoral / Doctor of Philosophy

Not available

A bioactive paper is a paper that can detect, capture and deactivate water and airborne pathogens. In this project, we presented a model "bioactive paper" made by attaching T4 bacteriophages to a cellulose substrate. T4 bacteriophages can be genetically engineered to possess copies of cellulose-binding modules (CBM) on their capsids. This allows them to bind specifically onto cellulose surfaces. Our model surface is a thin film of regenerated cellulose made by spin coating a glass or quartz substrate with a cellulose triacetate and subsequently hydrolyzing the surface back to cellulose. We successfully demonstrated the attachment of the CBM-T4 bacteriophages onto cellulose substrates by the phage viability test. The deposition kinetics were measured using an impinging jet apparatus combined with an evanescent wave light scattering (EWLS) system. We first tested the apparatus by using amidine latex particles deposited on the cellulose at different flow rates and found them to be in a good agreement with the constant potential double-layer model. The adhesion experiments were also performed in an impinging jet apparatus in which the CBM-T4 bacteriophages and the unassembled protein complexes from a suspension of 4.08 x 10 8 PFU/mL were allowed to diffuse to the cellulose surface, The competitive diffusion kinetics were again studied by the EWLS technique. For CBM-T4, the blocking time was found to be around 58 minutes and the maximum surface number density of phages was 5.9 x 1010 per m 2. / Key phrases: bioactive paper, cellulose film, cellulose binding module, bacteriophage T4, evanescent wave light scattering, unassembled protein complex, diffusion kinetics

A hole-collecting interlayer layer for organic solar cells, NiO, processed by atomic layer deposition (ALD) was studied. ALD-NiO film offered a novel alternative to efficient hole-collecting interlayers in conventional single-junction organic solar cells. Next, surface modifications with aliphatic amine group containing polymers for use as electron-collecting interlayers were studied. Physisorption of the polymers was found to lead to large reduction of the work function of conducting materials. This approach provides an efficient way to provide air-stable low-work function electrodes for organic solar cells. Highly efficient inverted organic solar cells were demonstrated by using the polymer surface modified electrodes. Lastly, charge recombination layers of the inverted tandem organic solar cells were studied. Efficient charge recombination layers were realized by using the ALD and the polymer surface modification. The charge recombination layer processed by ALD provided enhanced electrical and barrier properties. Furthermore, the polymer surface modification on the charge recombination layers showed large work function contrast, leading to improved inverted tandem organic solar cells. The inverted tandem organic solar cells with the new charge recombination layer showed fill factor over 70% and power conversion efficiency over 8%.

Thesis (Ph. D.)--University of Missouri-Columbia, 2004. / Typescript. Vita. Includes bibliographical references (leaves 222-228). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2004. / Typescript. Vita. Includes bibliographical references (leaves 222-228). Also available on the Internet.

Finding renewable sources of energy is becoming an increasingly important component of scientific research. Greater competition for existing sources of energy has strained the world’s supply and demand balance and has increased the prices of traditional sources of energy such as oil, coal, and natural gas. The experiment discussed in this paper is designed to identify and build an inexpensive and simple method for creating an effective organic solar cell.

The molecular design, synthesis, spectroscopic and photophysical characterization of a series of cyanostilbene-based compounds are studied in this thesis. The thermal, electrochemical and aggregation induced emission (AIE) properties of these cyanostilbene-based compounds, as well as their application in organic lighting-emitting diodes, live cell imaging, chemical vapor sensor were investigated. Chapter 1 gives a brief introduction on the aggregation-caused quenching (ACQ) behavior of the conventional organic luminogens and the discovery and proposed mechanism of AIE phenomenon. Furthermore, some examples and the applications of these AIE compounds will be discussed. In Chapter 2, triphenylamine- and carbazole-containing cyanostilbene-based derivatives are presented. From the examination of the emission profile, they are all AIE-active through comparison of the photoluminescence intensity in dissolved and in aggregated states. Additionally, the calculation of the enhancement ratio (I/I0 – 1) of each fluorophore was performed in order to quantify its AIE effect. One of our cyanostilbene-based luminogens has achieved an enhancement ratio with a value of 1128. This cyanostilbene-based luminogens has also shown good performance in OLED investigation. In addition to the OLEDs application, the selected cyanostilbene-based luminogens with solid-state emission, cell-permeability and reversible switch-on/off capability have illustrated the positive result in live-cell imaging and chemical vapor sensing. Conjugated polymer with high molecular weight is the superior option by overcoming the weaknesses of low-molecular-weight luminogens with excellent thin-film form ability and comparatively simple and inexpensive fabrication processes. The design and synthesis of the cyanostilbene-based polymeric chromophores are described in Chapter 3. The polymerization of the AIE-active diacetylene ligands by connection of trans-[Pt(PBu3)2] unit at both ends has successfully retained their AIE behavior. In contrast, the ACQ problem has occurred on the polymers with organic spacers and the AIE-active ligands. From the DFT calculation on the Pt polymers and the blue shift of emission spectra in high water content suggested that the AIE phenomenon of Pt polymers is probably originated from the elimination of the non-radiative intramolecular charge transfer (ICT) process. Owing to the high demand in red-emitting materials in the applications of electroluminescent devices, fluorescent sensing and bio-imaging, effort has been made to design a system with the new chromophores with donor (D) – acceptor (A) system and thus to synthesize phenothiazine (D)-containing cyanostilbene (A)-based derivatives which are depicted in Chapter 4. Consistent with the conventional AIE-active luminogens with a successively climb of photoluminescence intensities in response to the increase of water proportion, phenothiazine-containing cyanostilbene-based derivatives has exhibited a V-shape fashion of emission intensity. It suggests that the emission of chromophores started to be quenched due to the increase of solvent polarity, overriding that of the molecular aggregation when a “small” volume of water is being introduced. While aggregate formation was dominant from the addition of a “large” amount of poor solvent, less polar local environment was created which suppressed the non-radiative transition to the ICT state and intensified the emission efficiency. Phenothiazine (D) – cyanostilbene (A) system has created a series of red-emitting chromophores with great tunability for the sake of achieving the desired emission color and better emission efficiency. To functionalize these AIE-active cyanostilbene-based chromophores, pyridine group was attached to the compounds to take the advantage of its metal-chelating capability, which is discussed in Chapter 5. The AIE features of cyanostilbene-based compounds can be preserved after the introduction of the pyridyl unit. Even it possessed a weak photoluminescence in its dilute solution which suggest that the high electron delocalization within the molecule has rigidified the structure to some extent, it is transformed to a highly emissive state with a high proportion of water. The exclusive variation of emission behavior with obvious bathochromic shift and boost of emission spectrum in the presence of cadmium-(II) ion has demonstrated its potential metal ion sensing ability. Chapter 6 and 7 present the concluding remarks and the experimental data of the compounds of Chapter 2 to 5, respectively.

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.