Towards highly stable polymer electronics (Conference Presentation)

Organic semiconductors have evolved rapidly over the last decades and currently are considered as the next-generation technology for many applications, such as organic light-emitting diodes (OLEDs) in flat-panel displays (FPDs) and solid state lighting (SSL), and organic solar cells (OSCs) in clean renewable energy. This dissertation focuses mainly on OLEDs. Although the commercialization of the OLED technology in FPDs is growing and appears to be just around the corner for SSL, there are still several key issues that need to be addressed: (1) the cost of OLEDs is very high, largely due to the costly current manufacturing process; (2) the efficiency of OLEDs needs to be improved. This is vital to the success of OLEDs in the FPD and SSL industries; (3) the lifetime of OLEDs, especially blue OLEDs, is the biggest technical challenge. All these issues raise the demand for new organic materials, new device structures, and continued lower-cost fabrication methods. In an attempt to address these issues, we used solution-processing methods to fabricate highly efficient small molecule OLEDs (SMOLEDs); this approach is costeffective in comparison to the more common thermal vacuum evaporation. We also successfully made efficient indium tin oxide (ITO)-free SMOLEDs to further improve the efficiency of the OLEDs. We employed the spin-dependent optically-detected magnetic resonance (ODMR) technique to study the luminescence quenching processes in OLEDs and organic materials in order to understand the intrinsic degradation mechanisms. We also fabricated polymer LEDs (PLEDs) based on a new electron-accepting blue-emitting polymer and studied the effect of molecular weight on the efficiency of PLEDs. All these studies helped us to better understand the underlying relationship between the organic semiconductor materials and the OLEDs’ performance, and will subsequently assist in further enhancing the efficiency of OLEDs. With strongly improved device performance (in addition to other OLEDs' attributes such as mechanical flexibility and potential low cost), the OLED technology is promising to successfully compete with current technologies, such as LCDs and inorganic LEDs.

Sputtered transparent electrodes for optoelectronic devices: Induced damage and mitigation strategies

Admittance Spectroscopic analysis was applied to study the effect of LiF buffer layer and to model the equivalent circuit for poly(2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV)-based polymer light emitting diodes (PLEDs) with the LiF cathode buffer layer. The single layer device with ITO/MEH-PPV/Al structure can be modeled as a simple combination of two resistors and a capacitor. Insertion of a LiF layer at the Al/MEH-PPV interface shifts the lowest unoccupied molecular orbital (LUMO) level and the vacuum level of the MEH-PPV layer as a result of which the barrier height for electron injection at the Al/MEH-PPV interface is reduced. The admittance spectroscopic analysis of the devices with the LiF cathode buffer layer shows reduction in contact resistance (RC), parallel resistance (RP) and increment in parallel capacitance (CP).

Organic semiconductors devices, such as, organic solar cells (OSCs), organic light-emitting diodes (OLEDs) and organic field-effect transistors (OFETs) have drawn increasing interest in recent decades. As organic materials are flexible, light weight, and potentially low-cost, organic semiconductor devices are considered to be an alternative to their inorganic counterparts. This dissertation will focus mainly on OSCs and OLEDs. As a clean and renewable energy source, the development of OSCs is very promising. Cells with 9.2% power conversion efficiency (PCE) were reported this year, compared to < 8% two years ago. OSCs belong to the so-called third generation solar cells and are still under development. While OLEDs are a more mature and better studied field, with commercial products already launched in the market, there are still several key issues: (1) the cost of OSCs/OLEDs is still high, largely due to the costly manufacturing processes; (2) the efficiency of OSCs/OLEDs needs to be improved; (3) the lifetime of OSCs/OLEDs is not sufficient compared to their inorganic counterparts; (4) the physics models of the behavior of the devices are not satisfactory. All these limitations invoke the demand for new organic materials, improved device architectures, low-cost fabrication methods, and better understanding of device physics. For OSCs, we attempted to improve the PCE by modifying the interlayer between active layer/metal. We found that ethylene glycol (EG) treated poly(3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT: PSS) improves hole collection at the metal/polymer interface, furthermore it also affects the growth of the poly(3- hexylthiophene) (P3HT):phenyl-C61-butyric acid methyl ester (PCBM) blends, making the phase segregation more favorable for charge collection. We then studied organic/inorganic tandem cells. We also investigated the effect of a thin LiF layer on the hole-collection of copper phthalocyanine (CuPc)/C70-based small molecular OSCs. A thin LiF layer serves typically as the electron injection layer in OLEDs and electron collection interlayer in the OSCs. However, several reports showed that it can also assist in holeinjection in OLEDs. Here we first demonstrate that it assists hole-collection in OSCs, which is more obvious after air-plasma treatment, and explore this intriguing dual role. For OLEDs, we focus on solution processing methods to fabricate highly efficient phosphorescent OLEDs. First, we investigated OLEDs with a polymer host matrix, and enhanced charge injection by adding hole- and electron-transport materials into the system. We also applied a hole-blocking and electron-transport material to prevent luminescence quenching by the cathode. Finally, we substituted the polymer host by a small molecule, to achieve more efficient solution processed small molecular OLEDs (SMOLEDs); this approach is cost-effective in comparison to the more common vacuum thermal evaporation. All these studies help us to better understand the underlying relationship between the organic semiconductor materials and the OSCs and OLEDs’ performance and will subsequently assist in further enhancing the efficiencies of OSCs and OLEDs. With better efficiency and longer lifetime, the OSCs and OLEDs will be competitive with their inorganic counterparts.

The organic semiconductor materials which form Self-Assembled Monolayers (SAMs) on Indium Tin Oxide (ITO) surface have been synthesized and used in Organic Light Emitting Diode (OLED) applications. The synthesized molecules are bonded chemically to the hydrophilic and rough ITO surface and formed a new hydrophobic and smother surface of ITO by the effect of SAM formation. The synthesized SAM molecule is 4″, 4″″-[biphenyl-4,4″-diylbis(phenylimino)]dibiphenyl-4-carboxylic acid (MZ-187) that contains carboxylic acid head group to bond to ITO surface. The formation on ITO surface is analyzed by cyclic voltammetry (CV) and atomic force microscopy (AFM). Two configurations, ITO/SAM(MZ-187)/HTL/EML/LiF/Al (MZ187-OLED) and ITO/HTL/EML/LiF/Al (bare-OLED), are fabricated to investigate the effect of SAM layer on the performance of the OLED device. Current–voltage (I–V) characterization of OLED devices are carried out and the luminescence of the devices are measured by integrating sphere under nitrogen gas in a glow box system. The quantum efficiency is calculated to determine how to affects the SAM layers on OLEDs performance. As a consequence, it is determined that the OLED device containing MZ-187 SAM layer, a similar structure with N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD), is exhibited a better OLED performance compare to the device without SAM layer.

The recent rapid development of organic light-emitting diodes (OLEDs) has resulted in the commercialization of simple dot-matrix OLED displays.1 The great success of OLED devices has also introduced a brand new organic semiconductor. Now, we are in the process of designing the physical and chemical makeup of this new type of organic semiconductor. In this chapter, first we will briefly describe the OLED development from the 1960s to the 1980s. Second, we will define the new organic semiconductor especially utilized for OLED devices and clarify what the organic semiconductor is and how it differs from the conventional inorganic semiconductor. Then, we will review the recent OLED progress by taking the following aspects into consideration: the design of multilayer cell structures, the design of each molecular constituents, hole transport, electron transport, and emitter and dopant molecules. Finally, we will discuss the future prospects of OLEDs.

We propose a viable method of reducing the contact resistance of organic electronic devices by the formation of an organo-metal hybrid interlayer between a metal electrode and an organic semiconducting layer. The hybrid interlayer is produced by simultaneous deposition of the same materials as the electrode and the organic semiconductor, without any extra buffer layer. In such a hybrid interlayer, the metal clusters are uniformly dispersed on entangled organic surfaces so that they contribute significantly to the reduction of the contact resistance. The contact resistance is reduced by about a factor of seven. A simple theoretical model, based on the carrier accumulation and tunneling effects, well describes the essential features of the contact resistance as a function of the thickness of the hybrid interlayer.

Organic light-emitting devices (OLEDs) with various cathode structures were prepared on indium tin oxide (ITO) substrates by vacuum sublimation technique, and the effects of the device cathodes on the electroluminescence (EL) characteristics of OLEDs were studied in terms of the luminance, efficiency, driving voltage and threshold voltage. The results demonstrate that the optical and electrical performance of OLEDs depend on the properties of the devices' cathodes and the characteristics of the cathode–organic interface and the organic–organic interface. The optoelectrical performance of a device with composite cathodes is better than that of the devices with metal alloy and pure metal cathodes. The improvement in the device performance can be attributed to a more efficient electron injection at the cathode–organic interface, a better balanced hole and electron recombination in the light-emitting layer and fewer accumulated charges near the organic–organic interface.

Indium gallium zinc oxide (IGZO) thin-film transistors (TFTs) have attracted much attention because of their high electron mobility values (> 10 cm2/Vs) and because they can be processed at low temperature to produce large-area displays with the potential of low production costs. The IGZO TFTs require smaller RC signal delay with shorter channel length for high-resolution display applications. Therefore, it’s necessary to use self-aligned top-gate (TG) oxide TFT structure with smaller channel length for high-resolution, high-speed, low-power, and narrow-bezel displays. The IGZO TFTs also need good electrical stability under positive/negative bias temperature stress (P/NBTS) with decent TFT properties for peripheral gate driver integrated large size organic light emitting diode (OLED) TVs. TG IGZO TFTs for display applications such as OLED TVs typically use longer channel length (> 4 µm) due to negative threshold voltage (Vth) shift and Vth non-uniformity issues with smaller channel length, which is mainly caused by hydrogen diffusion near source/drain regimes during device integration. We fabricated TG IGZO TFTs by using Applied Material’s CVD/PVD tools to achieve excellent electrical stability and Vth uniformity by balancing oxygen and hydrogen diffusion into oxide channel layer such as IGZO. Suppressing carrier densities at the interface between gate insulator (GI) and IGZO by increasing oxygen diffusion with IGZO pre-annealing in air and TFT post anneal in air, and by minimizing vacuum annealing impact during GI deposition makes the IGZO TFTs more resistive with more positive Vth shift. On the other hands, more hydrogen diffusion into IGZO from GI, ILD, and passivation layers during device integration or TFT post annealing makes the IGZO TFTs more conductive with more negative Vth shift and worse Vth uniformity, but it helps to improve electrical stability with smaller Vth shift under PBTS by passivating defects inside IGZO. Therefore, there is trade-off between Vth uniformity and electrical stability due to the dominance of the diffusion between oxygen and hydrogen. By balancing the diffusion of oxygen and hydrogen, the IGZO TFTs can minimize negative Vth shift even with shorter channel for high-resolution display applications and achieve good electrical stability for pixel and peripheral gate driver circuits integrated in display panel. We successfully demonstrated excellent electrical properties such as high mobility (µFE), low sub-threshold slope (SS), good threshold voltage (Vth) position, and low off-leakage current from TG IGZO TFTs. The positions of Vth can be optimized by controlling carrier densities at the interface between GI and IGZO during device integration even with different GI temperature and power (Fig. 1). Here, GI type A is deposited at a low temperature of 225 ºC with a high RF power of 2400 W. GI type B is deposited at a high temperature of 270 ºC with a high RF power of 2400 W. GI type C is deposited at a high temperature of 270 ºC with a low RF power of 1600 W. In order to investigate the channel length dependency of Vth, Vth values were extracted from transfer characteristics at VDS = +1 V with various TFTs by fixing channel width of 12 µm and varying the channel length from 10 µm down to 3 µm. The differences between maximum Vth and minimum Vth, Vth (Max–Min), from GI type A, B, and C are 0.35 V, 0.48 V, and 1.20 V, respectively. Total resistance in TFTs was extracted from the measured IDS values by varying VGS from 12 V to 20 V with channel length from 10 µm down to 5 µm by transmission line method. Extracted 2∆L, the difference between mask channel length and effective channel length, from GI type A, B, and C are 0.78 µm, 0.87 µm, and 1.05 µm, respectively. The IGZO TFTs with higher GI power show better TFT uniformity than lower power GI without notable negative Vth shift and non-uniformity even with shorter channel length from 10 µm down to 3 µm by minimizing hydrogen diffusion into IGZO (Fig. 2). The IGZO TFTs with lower GI power show better stability under PBTS due to more hydrogen diffusion into IGZO. On the other hands, the IGZO TFTs show better stability under both PBTS and NBTS with higher GI temperature than lower temperature GI due to more hydrogen diffusion into IGZO (Fig. 3). Therefore, high power/high temperature GI is preferred for high-resolution mobile/VR displays considering short channel length effect and low power/high temperature GI is preferred for gate driver integrated OLED TVs considering stability, especially PBTS. Figure 1

A study on the electrical characteristics of InGaZnO thin-film transistor with HfLaO gate dielectric annealed in different gases

A challenge with the study of organic thin-film transistors rests in understanding the mechanism behind microstructure formation and its effects on the charge carrier mobility. Often, increased order in the molecular packing of the organic semiconductor film results in a superior mobility. The microstructure of the organic thin-films can be tuned by chemically modifying the surfaces using treatments, such as self-assembled monolayers (SAMs). In 2,8-difluoro-5,11-bis(triethylsilylethynyl) (diF-TES ADT) devices with pentafluorobenzenethiol (PFBT) treated contacts, for example, high mobility regions are produced on the gold contacts, due to large grain growth, while low mobility regions are formed off the contacts, as a result of small grain growth. To explore the mechanism driving this effect, we selectively choose fluorinated contact treatments which are able to introduce targeted interactions at interface between organic semiconductor and SAM-treated contacts. This allows us to isolate key mechanisms behind microstructure formation. Through selecting a specific number of fluorine atoms and placing them into key locations on a benzene thiol base, we can tune the field-effect mobility from 10–3 cm2V-1s-1 to 0.1 cm2V-1s-1 in this organic semiconductor. We combine FET measurements with GIXD data to correlate thin-film microstructure with electronic properties. To investigate the mechanism responsible for these differences in device performance, we perform first-principle density functional theory calculations, which allow us to quantify the interactions at the interfaces between the organic semiconductor and the various contact treatments. We find that Fluorine-Fluorine interactions between the organic semiconductor and the Fluorinated SAM used for contact treatment induce this unique microstructure. Through this knowledge one can selectively choose processing parameters to attain desired film microstructure and improve device performance.

: AlGaN/GaN high electron mobility transistors are promising for high frequency and high power application due to their unique properties. High-k dielectrics, such as Al2O3 and HfO2, are attractive materials which suppresses the gate leakage current of AlGaN/GaN high electron mobility transistors. Since the interface quality of AlGaN and high k dielectrics are critical to device performance, such as the threshold voltage and interface state density \201Dit\202, it is therefore necessary to understand that the relationship between interface chemistry and device performance is fundamental for examining optimization strategies for device applications. Firstly, the impact of various chemical pretreatments on AlGaN surface is studied. Then the interfaces formed upon atomic layer deposition \201ALD\202 of Al2O3 and HfO2 are investigated using in situ X-ray photoelectron spectroscopy \201XPS\202. The impacts of ALD of Al2O3 and HfO2 on native AlGaN are studied by capacitance voltage characterization. The XPS and device results uncover a high density of interface states. In situ N2 forming gas and O2 plasma pretreatments prior to ALD as optimization strategies are investigated using in situ XPS, LEED and C-V characterizations.

Steric modulation of thermally activated delayed fluorescence-type host for high quantum efficiency in blue phosphorescent organic light-emitting diodes

Modeling of bias-induced changes of organic field-effect transistor characteristics

The influence of carrier-injecting layers on the built-in potential of polymer light-emitting diodes (PLEDs) is analysed by means of electroabsorption spectroscopy. Two promising materials on which research has recently focused are: first, poly(ethylene-dioxythiophene)/poly(styrene sulphonic acid) (PEDOT:PSS), a doped conducting polymer employed as hole injector; and secondly, lithium fluoride (LiF), which has been shown to enhance electron injection of Al-based cathodes. In the first samples LEDs with an indium tin oxide (ITO) anode were compared to those incorporating a PEDOT:PSS layer (in an ITO/PEDOT:PSS bilayer anode). In the second set of samples the comparison was between LEDs with an aluminium cathode and those incorporating a LiF layer (in an Al/LiF bilayer cathode) as a function of LiF thickness. Electroabsorption spectroscopy results supported by work function measurements clearly prove that both PEDOT:PSS and LiF introduce a large reduction in the barrier height at the anode and cathode interfaces, respectively. The ensuing enhancement in carrier injection is considered to be responsible for the marked improvement in device performance (lower operating voltages, higher luminous efficiencies and longer lifetimes).