Design, synthesis, thin film deposition and characterization of new indium tin oxide anode functionalization/hole transport organic materials and their application to high performance organic light-emitting diodes

The primary goals of this dissertation were to understand the physical and chemical aspects of organic light-emitting diode (OLED) fundamentals, develop new materials as well as device structures, and enhance OLED electroluminescent (EL) response. Accordingly, this dissertation analyzes the relative effects of indium tin oxide (ITO) anode-hole transporting layer (HTL) contact vs. the intrinsic HTL material properties on OLED EL response. Two siloxane-based HTL materials, 4,4'-bis[(4″ -trichlorosilylpropyl-1″-naphthylphenylamino)biphenyl (NPB-Si2) and 4,4'-bis[(p-trichlorosilylpropylphenyl)phenylamino]biphenyl (TPD-Si2) have thereby been designed, synthesized and covalently bound to ITO surface. They afford a 250% increase in luminance and ∼50% reduction in turn-on voltage vs. comparable 4,4'-bis(1-naphthylphenylamino)biphenyl (NPB) HTL-based devices. These results suggest new strategies for developing OLED HTL structures, with focus on the anode-HTL contact.; Furthermore, archetypical OLED device structures have been refined by simultaneously incorporating the TPD-Si2 layer and a hole- and exciton-blocking/electron transport layer (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) in tris(8-hydroxyquinolato)aluminum(III) and tetrakis(2-methyl-8-hydroxyquinolinato)borate-based OLEDs. The refined device structures lead to high performance OLEDs such as green-emitting OLEDs with maximum luminance (Lmax) ∼ 85,000 cd/m2, power and forward external quantum efficiencies (eta p and etaext) as high as 15.2 lm/W and 4.4 +/- 0.5%, respectively, and blue-emitting OLEDs with Lmax 30,000 cd/m 2, and ∼5.0 lm/W and 1.6 +/- 0.2% etap and eta ext, respectively. The high performance is attributed to synergistically enhanced hole/electron injection and recombination efficiency.; In addition, molecule-scale structure effects at ITO anode-HTL interfaces have been systematically probed via a self-assembly approach. A series of silyltriarylamine precursors differing in aryl group and linker density have been designed and synthesized for this purpose. These precursors form conformal and largely pin-hole free self-assembled monolayers (SAMs) on the anode surface with A-level thickness control. Followed by deposition of a HTL on top of the SAMs, the probe molecules are placed precisely at the anode-HTL interface, resulting in varied hole injection magnitude and OLED response. The large interfacial molecular structure effects afford an approach to tuning OLED hole injection flux over one to two orders of magnitude, resulting in up to 3 fold variation in OLED brightness at identical bias and up to a 2 V driving voltage modulation at identical brightness.