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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 corroding calcium below. The introduction of up to three MLD interlayers of 12 nm each into the 48 nm barrier film laminate successfully mitigates stress issues and prevents the barrier from cracking. Using the three MLD interlayer configurations on glass, WVTRs of as low as 10-5 g/m²/d are measured at 38 °C and 32% relative humidity. On polymer barrier substrates, the calcium is evaporated onto the barrier stack and encapsulated with a cavity glass. In this configuration, the corroding calcium has space for expansion and gas release without affecting the underlying barrier film. In consequence, a WVTR of about 3 × 10-3 g/m²/d is measured for all samples independently of the number of MLD interlayers. In conclusion, a stabilization and preservation of the ALD barrier film against mechanical stress is achieved by the introduction of MLD interlayers into the inorganic nanolaminate. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Atomic layer deposited nanolaminates of alternating AlO x and TiO x 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. [ABSTRACT FROM AUTHOR]

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 5–10 nm for ALD processed Al 2 O 3 . In this work, we investigate the barrier performance of Al 2 O 3 films processed by ALD at 80 °C with trimethylaluminum and ozone as precursors. The coverage of defects in such films is investigated on a 5 nm thick Al 2 O 3 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 × 20 μm 2 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 100 nm, 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 15–25 nm 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 25 nm, 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 Al 2 O 3 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 25 nm. [ABSTRACT FROM AUTHOR]