Sami Hamwi

Transition Metal Oxides for Organic Electronics: Energetics, Device Physics and Applications

During the last few years, transition metal oxides (TMO) such as molybdenum tri-oxide (MoO(3) ), vanadium pent-oxide (V(2) O(5) ) or tungsten tri-oxide (WO(3) ) have been extensively studied because of their exceptional electronic properties for charge injection and extraction in organic electronic devices. These unique properties have led to the performance enhancement of several types of devices and to a variety of novel applications. TMOs have been used to realize efficient and long-term stable p-type doping of wide band gap organic materials, charge-generation junctions for stacked organic light emitting diodes (OLED), sputtering buffer layers for semi-transparent devices, and organic photovoltaic (OPV) cells with improved charge extraction, enhanced power conversion efficiency and substantially improved long term stability. Energetics in general play a key role in advancing device structure and performance in organic electronics; however, the literature provides a very inconsistent picture of the electronic structure of TMOs and the resulting interpretation of their role as functional constituents in organic electronics. With this review we intend to clarify some of the existing misconceptions. An overview of TMO-based device architectures ranging from transparent OLEDs to tandem OPV cells is also given. Various TMO film deposition methods are reviewed, addressing vacuum evaporation and recent approaches for solution-based processing. The specific properties of the resulting materials and their role as functional layers in organic devices are discussed.

Role of the deep-lying electronic states of MoO3 in the enhancement of hole-injection in organic thin films

The electronic structures of vacuum-deposited molybdenum trioxide (MoO3) and of a typical MoO3/hole transport material (HTM) interface are determined via ultraviolet and inverse photoelectron spectroscopy. Electron affinity and ionization energy of MoO3 are found to be 6.7 and 9.68 eV, more than 4 eV larger than generally assumed, leading to a revised interpretation of the role of MoO3 in hole injection in organic devices. The MoO3 films are strongly n-type. The electronic structure of the oxide/HTM interface shows that hole injection proceeds via electron extraction from the HTM highest occupied molecular orbital through the low-lying conduction band of MoO3.

Highly efficient simplified organic light emitting diodes

The authors report on highly efficient organic light emitting diodes (OLEDs) consisting of only two organic layers. The key to the simplification is the direct injection of holes into the wide band gap hole transport material 4,4′,4″-tris(N-carbazolyl)-triphenyl amine (highest occupied molecular orbital is 5.9eV) through an indium tin oxide/tungsten oxide (WO3) anode. Kelvin probe analysis has revealed an extremely high work function of 6.4eV for WO3. The efficiencies of the simplified OLEDs exceed 40lm∕W and 45cd∕A at a brightness of 100cd∕m2, unsurpassed by other comparably simple OLED devices. Therefore, our OLED architecture demonstrates highly efficient, yet easy to fabricate devices.

Charge generation layers comprising transition metal-oxide/organic interfaces: Electronic structure and charge generation mechanism

The energetics of an archetype charge generation layer (CGL) architecture comprising of 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), tungsten oxide (WO3), and bathophenanthroline (BPhen) n-doped with cesium carbonate (Cs2CO3) are determined by ultraviolet and inverse photoemission spectroscopy. We show that the charge generation process occurs at the interface between the hole-transport material (TCTA) and WO3 and not, as commonly assumed, at the interface between WO3 and the n-doped electron-transport material (BPhen:Cs2CO3). However, the n-doped layer is also essential to the realization of an efficient CGL structure. The charge generation mechanism occurs via electron transfer from the TCTA highest occupied molecular orbital level to the transition metal-oxide conduction band.

p-type doping efficiency of MoO3 in organic hole transport materials

We report on the p-type doping efficiency of molybdenum trioxide (MoO3) in the ambipolar organic charge transport material 4,4′-Bis(carbazol-9-yl)-biphenyl (CBP). Kelvin probe analysis is used to study the work function with increasing thickness of doped CBP layers with varied MoO3 concentration deposited on indium tin oxide (ITO). Based on the model of a one-sided abrupt (n+p) junction between ITO and the MoO3 doped CBP layer, the density of free holes has been determined. A surprisingly low p-type doping efficiency of less than 2% has been derived. Segregation and clustering of the MoO3 dopant could explain these results.

Indium-free transparent organic light emitting diodes with Al doped ZnO electrodes grown by atomic layer and pulsed laser deposition

We present highly efficient transparent organic light emitting diodes (OLEDs) with Al doped ZnO (AZO) electrodes prepared by atomic layer deposition and pulsed laser deposition (PLD). The power and current efficiencies exceed 27 lm/W and 44 cd/A at a brightness level of 100 cd/m2, respectively. At the same time, the transmissivity of the devices is above 73% in the visible part of the spectrum. Owing to an efficient WO3 buffer layer and an optimized PLD process for the deposition of the top AZO electrode, the OLEDs show leakage current densities as low as 3×10−5 mA/cm2 at a reverse bias of 6 V. Therefore, our study paves the way for indium-free, see-through OLED displays.

Highly efficient organic tandem solar cells using an improved connecting architecture

Tandem solar cells based on the combination of a poly(3-hexylthiophene-2,5-diyl):[6,6]-phenyl-C61-butyric acid methyl ester and a copper phthalocyanine:fullerene subcell are reported. By using a highly transparent, high-work function WO3 layer as part of the interconnecting system for the two subcells, the authors demonstrate stacked devices with power conversion efficiencies as high as 4.6%. The efficiency of the stacked devices is close to the sum of the efficiencies of the individual subcells.

Reliable thin film encapsulation for organic light emitting diodes grown by low-temperature atomic layer deposition

We report on highly efficient gas diffusion barriers for organic light emitting diodes (OLEDs). Nanolaminate (NL) structures composed of alternating Al2O3 and ZrO2 sublayers grown by atomic layer deposition at 80 °C are used to realize long-term stable OLED devices. While the brightness of phosphorescent p-i-n OLEDs sealed by a single Al2O3 layer drops to 85% of the initial luminance of 1000 cd/m2 after 1000 h of continuous operation, OLEDs encapsulated with the NL retain more than 95% of their brightness. An extrapolated device lifetime substantially in excess of 10 000 h can be achieved, clearly proving the suitability of the NLs as highly dense and reliable thin film encapsulation of sensitive organic electronic devices.

A strategy towards p-type doping of organic materials with HOMO levels beyond 6 eV using tungsten oxide

The authors present a concept to p-dope organic hole transport materials with highest occupied molecular orbital (HOMO) levels on the order of 6 eV (e.g.4,4′,4″-tris(N-carbazolyl)-triphenylamine (TCTA) or 4,4′-bis(carbazol-9-yl)biphenyl (CBP)) by using WO3 as acceptor. Owing to its large work function, WO3 allows for efficient electron transfer from organic semiconductors with HOMO levels in this region. The effect of p-type doping is evidenced by optical absorption spectroscopy, electrical transport characteristics and Kelvin probe analysis. Moreover, OLED devices have been realized which exhibit 30% enhanced power efficiency due to the p-type doping. The results are expected to have a significant impact on the development of organic (opto-)electronic devices.

An organic p-i-n homojunction as ultra violet light emitting diode and visible-blind photodiode in one

Organic p-i-n homojunctions that function both as ultra violet light emitting diode (peak wavelengths around 375 nm and 415 nm) and visible-blind photodiode are reported. They are considered as the organic counterpart to what has exclusively been known from inorganic semiconductors, as yet. The diodes are based on the ambipolar material 4,4′-Bis(carbazol-9-yl)-biphenyl (CBP) which is p- and n-type doped adjacent to the electrodes. We study the emission characteristics of the p-i-n homojunction for varied doping concentrations and subsequently focus on its characteristics as photodiode. A superlinear relation of photocurrent and incident light intensity is found and attributed to an intensity-dependent photoconductivity.