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The synthesis of novel asymmetrically substituted cobalt complexes of the type [Co(CO)(NO)(NHC)(PR3)] (NHC = iPr2Im, PR3 = PMe3 (1), PEt3(2), PHiPr2 (3); PR3 = PMe3;, NHC = Me2ImMe (4), MeiPrIm (5), MetBuIm (6), iPr2ImMe (7); R2Im = 1,3-dialkylimidazolin-2-ylidene) is reported. These complexes are stabilized by N-heterocyclic carbene (NHC), phosphine, carbonyl, and nitrosyl ligands and have been synthesized from the reaction of a NHC-substituted precursor of the type [Co(CO)2(NO)(NHC)] and the corresponding phosphine. The synthesis of [Co(CO)(NO)(MetBuIm)(PMe3)] (6) and [Co(CO)(NO)(iPr2ImMe)(PMe3)] (7) proceeds in a thermal reaction even at room temperature by quantitative replacement of one carbonyl with a phosphine ligand. All of the other complexes were synthesized using photochemical conditions. Complexes 1–6 have been characterized by elemental analysis, IR spectroscopy, and multinuclear NMR spectroscopy and in some cases by X-ray crystallography. All complexes are volatile, are stable upon sublimati...

Aluminum oxide (Al 2 O 3 ) thin films grown by atomic layer deposition (ALD) at low temperatures exhibit low film densities, and therefore, may not meet the requirements for demanding barrier applications. In this work, a novel approach is presented to obtain improved film densities by short-term thermal treatments while keeping the overall low thermal budget of the deposition process. For that purpose, millisecond flash lamp annealing (FLA) was directly integrated into the ALD process, enabling the thermal treatment of the growing films not only subsequent to the deposition process but already right during the stage of film growth. By applying this in situ FLA after every single ALD cycle, the density of Al 2 O 3 films grown at a substrate temperature of 75 °C could be increased from 2.8 g/cm 3 up to 3.1 g/cm 3 . However, this 10% increase in film density was not related to an ordinary film densification. Instead, the studies reveal that in situ FLA promoted an enhanced and denser film growth, most probably by directly affecting the surface chemistry of the ALD process. The enhanced film growth was observed in terms of a 25% increase in the mass gain per cycle, reaching a level comparable to pure ALD at a deposition temperature of 250 °C. Furthermore, the application of in situ FLA also resulted in an improved film composition, increased refractive indices, higher dielectric constants and reduced leakage currents. The presence of molecular hydrogen during the FLA treatments led to an even further improved mass gain per cycle, film composition and dielectric constant. Despite the FLA treatments the films remained amorphous. In addition, the film densities obtained by the application of in situ FLA were not achieved by conventional post deposition annealing with temperatures up to 600 °C.

Atomic layer deposited nanolaminates of alternating AlOx and TiOx thin-films are investigated as moisture barriers for organic electronic devices. Direct encapsulation on organic light emitting diodes (OLEDs) is tested in aging experiments and compared to calcium corrosion tests of equivalent barrier films. This allows for a direct assessment of moisture barrier performance in simple as well as more complex systems. Thickness variations are performed for the nanolaminate single and total layer thickness, with an optimum single layer thickness of 1–2 nm observed. This correlates to the maximum number of dyads once completely closed single layers are produced. For large single layer thickness and low dyad count, strong lateral diffusion from the edges occurs in the OLEDs, which likely correlates to poor mechanical stability. At optimum single layer thickness, barriers remain mechanically and chemically stable up to 100 nm total thickness. OLEDs encapsulated with such nanolaminate barriers show no significant degradation after 2500 h of continuous aging.

The water vapor barrier properties of low-temperature atomic layer deposited (ALD) AlOx thin-films are observed to be unstable if exposed directly to high or even ambient relative humidities. Upon exposure to humid atmospheres, their apparent barrier breaks down and their water vapor transmission rates (WVTR), measured by electrical calcium tests, deteriorate by several orders of magnitude. These changes are accompanied by surface roughening beyond the original thickness, observed by atomic force microscopy. X-ray reflectivity investigations show a strong decrease in density caused by only 5 min storage in a 38 °C, 90% relative humidity climate. We show that barrier stabilities required for device applications can be achieved by protection layers which prevent the direct contact of water condensing on the surface, i.e., the sensitive ALD barrier. Nine different protection layers of either ALD materials or polymers are tested on the barriers. Although ALD materials prove to be ineffective, applied polymers seem to provide good protection independent of thickness, surface free energy, and deposition technique. A glued-on PET foil stands out as a low-cost, easily processed, and especially stable solution. This way, 20 nm single layer ALD barriers for organic electronics are measured. They yield reliable WVTRs down to 2×10(-5) g(H2O) m(-2) day(-1) at 38 °C and 90% relative humidity, highlighting the great potential of ALD encapsulation.

Organic devices like organic light emitting diodes (OLEDs) or organic solar cells degrade fast when exposed to ambient air. Hence, thin-films acting as permeation barriers are needed for their protection. Atomic layer deposition (ALD) is known to be one of the best technologies to reach barriers with a low defect density at gentle process conditions. As well, ALD is reported to be one of the thinnest barrier layers, with a critical thickness – defining a continuous barrier film – as low as 5–10nm for ALD processed Al2O3. In this work, we investigate the barrier performance of Al2O3 films processed by ALD at 80°C with trimethylaluminum and ozone as precursors. The coverage of defects in such films is investigated on a 5nm thick Al2O3 film, i.e. below the critical thickness, on calcium using atomic force microscopy (AFM). We find for this sub-critical thickness regime that all spots giving raise to water ingress on the 20×20μm2 scan range are positioned on nearly flat surface sites without the presence of particles or large substrate features. Hence below the critical thickness, ALD leaves open or at least weakly covered spots even on feature-free surface sites. The thickness dependent performance of these barrier films is investigated for thicknesses ranging from 15 to 100nm, i.e. above the assumed critical film thickness of this system. To measure the barrier performance, electrical calcium corrosion tests are used in order to measure the water vapor transmission rate (WVTR), electrodeposition is used in order to decorate and count defects, and dark spot growth on OLEDs is used in order to confirm the results for real devices. For 15–25nm barrier thickness, we observe an exponential decrease in defect density with barrier thickness which explains the likewise observed exponential decrease in WVTR and OLED degradation rate. Above 25nm, a further increase in barrier thickness leads to a further exponential decrease in defect density, but an only sub-exponential decrease in WVTR and OLED degradation rate. In conclusion, the performance of the thin Al2O3 permeation barrier is dominated by its defect density. This defect density is reduced exponentially with increasing barrier thickness for alumina thicknesses of up to at least 25nm.

Highly efficient nanolaminate diffusion barriers made of TiO 2 /Al 2 O 3 multilayers using low temperature atomic layer deposition optimized for organic light emitting diodes are presented. Water vapour transmission rates (WVTR) show values of the order of 10 −3 g/m 2 /d at 38 °C, 90% RH on planarized PEN webs (pPEN) when ozone is used as the oxidizing precursor for Al 2 O 3 deposition. OLED encapsulated with such diffusion barriers display few dark spots observed over 2000 h after deposition and for aging under ambient conditions. Diffusion barriers deposited using water as the oxidizing precursor for Al 2 O 3 result in at least 10 times lower WVTR on pPEN webs (10 −4 g/m 2 /d). However, these water based diffusion barriers are incompatible with OLEDs such that the latter show extensive black spot formation (areas of no visible luminescence) immediately after deposition. Finally through the growth of these initial black spots, more than 40% loss in initial luminescence occurs after merely 900 h of operation. In this report, we introduce a new methodology for OLED encapsulation using a two step process where 10 nm thick ozone Al 2 O 3 based nanolaminate diffusion barrier is followed by a 90 nm thick water Al 2 O 3 based diffusion barrier (keeping TiO 2 precursors always the same). With this novel diffusion barrier stack, no visible black spot growth is observed over 2000 continuous operation hours under ambient conditions. Simultaneously, high OLED luminescence representing 90% of the initial luminescence value, which is measured at t = 0 is maintained after 2000 h of operation. Low WVTR values in the 10 −4 g/m 2 /d range on pPEN webs are consistently measured in these essentially water based barrier layers with only 10 nm thick starting ozone Al 2 O 3 based nanolaminate diffusion barriers. The results reported here have implications on developing methodologies for ultra high performance, OLED compatible diffusion barriers by ALD.

Atomic Layer Deposition (ALD) is a particular thin film deposition technology which is based on alternating saturated surface reactions. As a result, the film growth proceeds in a self-limiting manner enabling the deposition of thin films with excellent thickness control, uniformity, and conformity. Although a large number of materials have been deposited by ALD so far for various applications, there are still some challenges in ALD. The deposition temperatures in ALD are typically lower compared to CVD due to the limited thermal stability of ALD precursors. As a consequence of the lower energy available for film formation the films may not meet the properties needed for application. In these cases a post deposition annealing is required to improve the film properties, e.g. to obtain the desired film structure, density, or purity. However, this high temperature processing is often impracticable due to a restricted thermal budget of the substrate, in particular when coating temperature sensitive substrates. Secondly, the reactants of an ALD process, e.g. oxygen, may react with the substrate itself leading to the formation of a parasitic interfacial layer. In order to avoid this issue, the proper choice of reactants or the use of an alternative deposition technique is essential. Furthermore, many ALD processes suffer from substrate inhibited film growth accompanied by inefficient precursor consumption and the formation of films with unfavorable properties. Finally, there are materials of interest, e.g. titanium, which so far can not be deposited by thermal ALD at all. These limitations may be overcome by the application of flash lamp annealing (FLA) in ALD. In FLA the substrate is exposed to a light flash with durations typically in the millisecond range. The light energy is absorbed within the top layers of the sample causing a rapid heating of the surface near region. On the contrary, the bulk material experiences no or only moderate heating. Consequently, FLA is a suitable technology to power high temperature processes even on temperature sensitive substrates. The film growth in flash lamp enhanced ALD is induced by this effect. Thereby, each process cycle consist of both a precursor pulse and the irradiation of the substrate with a light flash. During each single flash the surface temperature exceeds the threshold temperature which is required to achieve the thermal decomposition of adsorbed precursor molecules or to activate chemical reactions between the adsorbed precursor molecules and a second reactant. The film growth proceeds step-by-step and thus the film thickness can be controlled by varying the number of cycles. In addition, FLA in each cycle results in the periodical annealing of the already grown film and hence may lead to an improved film quality. Consequently, flash lamp enhanced ALD has a high potential for the realization of single-source processes, for the reduction of growth delay in the initial phase of film growth, for the deposition of high purity thin films, and for the deposition of new materials. In this work the principle of flash lamp enhanced ALD will be presented in detail, the technology will be reviewed and classified. Thereafter, we will give an overview about our studies on the flash enhanced ALD of aluminum-, ruthenium-, and tantalum-based thin films. These depositions were realized by flashing periodically on a substrate during the precursor pulses. We will show that the film growth is induced by the flash heating and the processes exhibits typical ALD characteristics. The obtained relations between flash parameters and film growth parameters will be discussed with the use of simulation results illustrating the temperature profile during the FLA treatment. Moreover, this work addresses the potentials of this technology as well as the technical challenges.

The paper presents atomic layer deposition (ALD) processes and process integration for the deposition of insulating liners, copper diffusion barriers, and seed layers for direct copper plating in high aspect ratio (>20:1) through silicon vias. A TaN-based copper diffusion barrier was deployed on an aluminum oxide insulating liner. The latter has the potential to act also as a dielectric barrier against copper diffusion according to BTS and TVS measurements. Furthermore, ruthenium ALD films applied as seed layers for direct copper plating were deposited with an intermediate annealing step to improve film adhesion and ensure the deposition of thick films without any delamination. The step coverage of the presented ALD processes was confirmed by SEM measurements on cross-sections of coated TSV structures. Finally a subsequent electrochemical deposition (ECD) of copper was conducted revealing the satisfying functionality of the Ru seed layer.

Doping allows us to control the majority and minority charge carrier concentration in organic field-effect transistors. However, the precise mechanism of minority charge carrier generation and transport in organic semiconductors is largely unknown. Here, the injection of minority charge carriers into n-doped organic field-effect transistors is studied. It is shown that holes can be efficiently injected into the transistor channel via Zener tunneling inside the intrinsic pentacene layer underneath the drain electrode. Moreover, it is shown that the onset of minority (hole) conduction is shifted by lightly n-doping the channel region of the transistor. This behavior can be explained by a large voltage that has to be applied to the gate in order to fully deplete the n-doped layer as well as an increase in hole trapping by inactive dopants.

Within this work, flash lamp annealing (FLA) is utilized to thermally enhance the film growth in atomic layer deposition (ALD). First, the basic principles of this flash-enhanced ALD (FEALD) are presented in detail, the technology is reviewed and classified. Thereafter, results of our studies on the FEALD of aluminum-based and ruthenium thin films are presented. These depositions were realized by periodically flashing on a substrate during the precursor exposure. In both cases, the film growth is induced by the flash heating and the processes exhibit typical ALD characteristics such as layer-by-layer growth and growth rates smaller than one A/cycle. The obtained relations between process parameters and film growth parameters are discussed with the main focus on the impact of the FLA-caused temperature profile on the film growth. Similar, substrate-dependent growth rates are attributed to the different optical characteristics of the applied substrates. Regarding the ruthenium deposition, a single-source process was realized. It was also successfully applied to significantly enhance the nucleation behavior in order to overcome substrate-inhibited film growth. Besides, this work addresses technical challenges for the practical realization of this film deposition method and demonstrates the potential of this technology to extend the capabilities of thermal ALD. © The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. [DOI: 10.1149/2.0301507jss] All rights reserved.

The inversion field-effect transistor is the basic device of modern microelectronics and is nowadays used more than a billion times on every state-of-the-art computer chip. In the future, this rigid technology will be complemented by flexible electronics produced at extremely low cost. Organic field-effect transistors have the potential to be the basic device for flexible electronics, but still need much improvement. In particular, despite more than 20 years of research, organic inversion mode transistors have not been reported so far. Here we discuss the first realization of organic inversion transistors and the optimization of organic depletion transistors by our organic doping technology. We show that the transistor parameters—in particular, the threshold voltage and the ON/OFF ratio—can be controlled by the doping concentration and the thickness of the transistor channel. Injection of minority carriers into the doped transistor channel is achieved by doped contacts, which allows forming an inversion layer., Inversion type transistors – which are widely used in silicon-based industries – are thought to not be obtainable in organic devices. Lüssem et al. realize the first inversion organic field-effect transistor by doping at the source and drain contacts without degrading its ON/OFF ratio.

For thermal ALD Ta"xN"yC"z films improved growth behaviour and Cu diffusion barrier performance are demonstrated by applying a plasma treatment prior to film deposition, in particular on low-k dielectrics. Two different kinds of ALD processes for depositing thermal ALD Ta"xN"yC"z films are applied in this study, involving either TBTDET or PDMAT as a precursor. Ammonia is used as a reactant and Ar as a purging gas in both processes. Within the experiment, two types of pre-treatments prior to ALD are investigated: a wet-chemical pre-treatment using diluted (0.5%) HF, and plasma pre-treatments using Ar/H"2 or N"2 plasmas. It is examined by transmission electron microscopy (TEM) from a microstuctural perspective whether improved growth behaviour of thermal ALD Ta"xN"yC"z films can be achieved by applying a plasma treatment prior to film deposition. The Cu diffusion barrier properties of 10-15nm ALD TaNC films are then evaluated by bias temperature stress (BTS) and triangular voltage sweep (TVS) measurements on metal-insulator-semiconductor (MIS) test structures, after annealing at up to 600^oC under H"2/N"2 atmosphere. The results imply that, from a process side, thermal ALD TaNC films can intrinsically achieve a Cu diffusion barrier performance similar to PVD TaN. However, if no treatment was applied, Cu drift occurred.

The interest in vertical organic transistors as a means to overcome the limitations of conventional organic field-effect transistors (OFETs) has been growing steadily in recent years. Current vertical architectures, however, often suffer from a lack of parameter control, as they are limited to certain materials and processing techniques, making a controlled shift of, e.g., the transistor threshold voltage difficult. In this contribution, we present a vertical OFET (VOFET) operating in the inversion regime. By varying the thickness or doping concentration of a p-doped layer in an otherwise n-type VOFET, we are able to shift the threshold voltage in a controlled manner from 1.61 V (for a normal n-type VOFET) to 4.83 V (for the highest doping concentration of 50 mol. %). Furthermore, it is found that low doping concentrations of 20 mol. % can improve the Off state of the VOFET through reduction of the source-drain leakage current.

Diffusion barrier stacks for the encapsulation of organic electronics made from inorganic nanolaminates of Al2O3 and TiO2 with aluminum alkoxide interlayers have been deposited by atomic layer deposition (ALD) and molecular layer deposition (MLD). As a part of the MLD process development, the deposition of aluminum alkoxide with low a density of about 1.7 g/cm3 was verified. The ALD/MLD diffusion barrier stack is meant to be deposited either on a polymer film, creating a flexible barrier substrate, or on top of a device on glass, creating a thin-film encapsulation. In order to measure the water vapor transmission rate (WVTR) through the barrier, the device is replaced by a calcium layer acting as a water sensor in an electrical calcium test. For the barrier stack applied as thin-film encapsulation on glass substrates, high resolution scanning electron microscopy investigations indicate that the inorganic nanolaminates without MLD interlayers are brittle as they crack easily upon the stress induced by the ...

The importance of O3 pulse duration for encapsulation of organic light emitting diodes (OLEDs) with ultra thin inorganic atomic layer deposited Al2O3 layers is demonstrated for deposition temperatures of 50 °C. X-ray reflectivity (XRR) measurements show that O3 pulse durations longer than 15 s produce dense and thin Al2O3 layers. Correspondingly, black spot growth is not observed in OLEDs encapsulated with such layers during 91 days of aging under ambient conditions. This implies that XRR can be used as a tool for process optimization of OLED encapsulation layers leading to devices with long lifetimes.