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Perovskites are currently attracting extensive research interest as a wavelength-tunable lasing material. As a first step toward electrically pumped lasers, numerous investigations have recently reported amplified spontaneous emission (ASE) of optically pumped perovskites with remarkably low thresholds. Here, we investigate the optical aspects of perovskite ASE, to establish the design principle of materials and devices. We show that compared to solution-processed CsPbBr3, vacuum deposition yields superior ASE characteristics with a threshold of 35 μJ/cm2. The optical loss (Rloss) during lateral photon propagation in the waveguide mode is identified as a key parameter to determine the ASE quality. With spatially resolved photoluminescence, we determine Rloss as 40 and >1000 cm-1 for vacuum and solution-processed perovskites, respectively. We present a comprehensive model that relates ASE, gain length, optical loss, temperature, and density of states. Finally, we succeed in demonstrating ASE in perovskite samples with metal electrodes, mimicking a diode architecture for electrical pumping. Optical spacer layers are shown to play a crucial role in preventing metal absorption loss in waveguide modes.

Thermal evaporation is a well-established and versatile method for the deposition of large-area, uniform, high-quality semiconducting layers in a broad range of optoelectronic applications. Despite extensive investigation of deposition by thermal evaporation in the field of perovskite solar cells, solution-processed perovskite devices still significantly outperform those fabricated by thermal evaporation, particularly in the case of methylammonium-free perovskite compositions. Herein, we fabricate and investigate thermally evaporated Cs0.1FAxPbI2+xBr0.1 perovskite solar cells and explore the effects of FAI deficiency or excess and that of post-annealing on the perovskite layer properties and device performance. We find that annealing can significantly improve the optical and structural properties of FAI-poor perovskite layers, resulting in a stark enhancement of their photovoltaic performance. While stoichiometric devices are also improved, albeit to a lesser degree, by post-annealing, this process is found to be detrimental for the FAI-rich devices, resulting in a drastic loss of performance. We show that annealed stoichiometric devices with an optimised active layer thickness result in power conversion efficiencies of up to 16.6%, approaching the performance of solution-processed devices of similar composition.

Metal halide perovskites are the first solution processed semiconductors that can compete in their functionality with conventional semiconductors, such as silicon. Over the past several years, perovskite semiconductors have reported breakthroughs in various optoelectronic devices, such as solar cells, photodetectors, light emitting and memory devices, and so on. Until now, perovskite semiconductors face challenges regarding their stability, reproducibility, and toxicity. In this Roadmap, we combine the expertise of chemistry, physics, and device engineering from leading experts in the perovskite research community to focus on the fundamental material properties, the fabrication methods, characterization and photophysical properties, perovskite devices, and current challenges in this field. We develop a comprehensive overview of the current state-of-the-art and offer readers an informed perspective of where this field is heading and what challenges we have to overcome to get to successful commercialization. published

Recently, organic solar cells have demonstrated high power conversion efficiencies, but extrinsic device stability remains to be a challenge. Often, delamination of the cathode upon water ingress leads to a massive active area loss and to a strong decrease in efficiency. We present highly efficient organic solar cells with an oligothiophene-based donor and two different cathodes. Devices are aged at four different climates under continuous illumination. Al and MoO3/Cr/Al cathodes are compared. Additional interlayers are introduced for enhanced cathode adhesion. Aging in different climates reveals a strong dependency of the degradation speed on absolute humidity for standard Al cathodes. However, using additional interlayers, degradation seems to be almost decoupled from the applied climate and device degradation is slowed immensely. Parallel WVTR measurements of the AlOx barrier allow for the assessment of absolute water quantities until devices are degraded to half of their initial efficiency: 24gm2 are found for standard Al cathodes, while devices with additional interlayers reach 58gm2. This difference is related to a completely different aging behavior, which trades strong short-circuit current density losses for moderate fill-factor losses.

Flexible aluminum moisture barrier films are shown to meet ultra-barrier requirements with water vapor transmission rates as low as 1*10−4 g/m2/day at 38 °C and 90% R.H. These low transmission rates are achieved by lamination of two films that are independently processed on individual substrates. The integration in organic electronic devices like organic solar cells or OLEDs is particularly easy in a single lamination step, since an existing aluminum electrode can be utilized as one half of the moisture barrier. The resulting laminate maintains flexibility of the device and improves the barrier quality by an order of magnitude compared to conventional stacking of two barriers. Organic solar cells with this type of encapsulation are manufactured and aged in controlled climate. They do not exhibit significant extrinsic degradation.

Flexible transparent barrier films are required in various fields of application ranging from flexible, transparent food packaging to display encapsulation. Environmentally friendly, waterborne polymer–clay nanocomposites would be preferred but fail to meet in particular requirements for ultra high water vapor barriers. Here we show that self-assembly of nanocomposite films into one-dimensional crystalline (smectic) polymer–clay domains is a so-far overlooked key-factor capable of suppressing water vapor diffusivity despite appreciable swelling at elevated temperatures and relative humidity (R.H.). Moreover, barrier performance was shown to improve with quality of the crystalline order. In this respect, spray coating is superior to doctor blading because it yields significantly better ordered structures. For spray-coated waterborne nanocomposite films (21.4 μm) ultra high barrier specifications are met at 23 °C and 50% R.H. with oxygen transmission rates (OTR) < 0.0005 cm3 m–2 day–1 bar–1 and water vapor ...

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.

OLEDs and organic photovoltaic (OPV) devices require encapsulation from water vapor using a permeation barrier system. As a benchmark for barrier quality, often only a single number is provided as water vapor transmission rate. However, this value is highly dependent on the aging climate. So far, little scientific effort has been undertaken to characterize ultrahigh moisture barriers at different temperatures and relative humidities. We present Ca-test studies on sputtered Zinc-Tin-Oxide and atomic layer deposited AlOx barriers in extensively varied climates. Relative humidities are changed at constant temperatures, and temperatures are changed at constant absolute humidity. We find Henry's law to apply for sorption and discover a fundamental change of the diffusion regime with time related to the interface between the test and the barrier thin-film.

We investigate the degradation of organic solar cells based on an oligothiophene (DCV5T-Me) small molecule donor and the acceptor C60. Two different flexible, transparent bottom electrode types are employed: a transparent metal electrode (TME) and silver nanowires (AgNWs). They exhibit high optical transparency up to 86% and a sheet resistance as low as 12Ω/□. Power conversion efficiencies of 7.0%, 5.7%, and 7.2% on TME, AgNWs, and indium tin oxide (ITO, reference) are reached, respectively. The solar cells are protected against moisture ingress utilizing a flexible alumina thin-film, exhibiting water vapor transmission rates down to 3 × 10(-5) g m(-2) day(-1) at 38 °C and 90% relative humidity (RH). Implementation of this ultrabarrier as top and bottom encapsulation enables fabrication of fully flexible devices. A decrease in PCE to 80% of initial values is observed after 1000 ± 50 h on flexible, encapsulated TME but only 20 ± 5 h on AgNWs in a climate of 38 °C/50% RH. Degradation in AgNW-based devices is attributed to electrode decomposition.

Oxygen-free, transparent, and insulating thin films at fabrication temperatures below 100 °C are important for sensitive materials and interfaces, like organic electronics. In this work, a capacitive coupled plasma-enhanced atomic layer deposition process of aluminum nitride with trimethylaluminum as a precursor and a mixture of hydrogen/nitrogen as the reactive gas was studied at 80 and 200 °C. The film properties were characterized by spectroscopic ellipsometry, x-ray photoelectron spectroscopy, scanning electron microscopy, and electrical measurements. The growth per cycle stayed constant at around 1 A, and the refractive index decreased slightly from 1.97 at 200 °C to 1.93 at 80 °C. While the AFM surface roughness was below 0.5 nm at 80 °C deposition temperature, scanning electron microscopy images reveal blister generation at 200 °C on silicon. The x-ray photoemission spectroscopy measurements show a layer composition of Al:N of 1.0:0.9 with a few percent of oxygen and carbon, indicating good air stability and reasonable stoichiometry. The metal-insulator-metal capacitance measurements showed a dielectric constant of 11 at both temperatures. The water vapor transmission rate for a 20 nm thick film on polyethylene naphthalate films was lower than 0.5 mg/(m2⋅day) at 38 °C/90%.Oxygen-free, transparent, and insulating thin films at fabrication temperatures below 100 °C are important for sensitive materials and interfaces, like organic electronics. In this work, a capacitive coupled plasma-enhanced atomic layer deposition process of aluminum nitride with trimethylaluminum as a precursor and a mixture of hydrogen/nitrogen as the reactive gas was studied at 80 and 200 °C. The film properties were characterized by spectroscopic ellipsometry, x-ray photoelectron spectroscopy, scanning electron microscopy, and electrical measurements. The growth per cycle stayed constant at around 1 A, and the refractive index decreased slightly from 1.97 at 200 °C to 1.93 at 80 °C. While the AFM surface roughness was below 0.5 nm at 80 °C deposition temperature, scanning electron microscopy images reveal blister generation at 200 °C on silicon. The x-ray photoemission spectroscopy measurements show a layer composition of Al:N of 1.0:0.9 with a few percent of oxygen and carbon, indicating good air sta...

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.

Blending organic electron donors and acceptors yields intermolecular charge-transfer states with additional optical transitions below their optical gaps. In organic photovoltaic devices, such states play a crucial role and limit the operating voltage. Due to its extremely weak nature, direct intermolecular charge-transfer absorption often remains undetected and unused for photocurrent generation. Here, we use an optical microcavity to increase the typically negligible external quantum efficiency in the spectral region of charge-transfer absorption by more than 40 times, yielding values over 20%. We demonstrate narrowband detection with spectral widths down to 36 nm and resonance wavelengths between 810 and 1,550 nm, far below the optical gap of both donor and acceptor. The broad spectral tunability via a simple variation of the cavity thickness makes this innovative, flexible and potentially visibly transparent device principle highly suitable for integrated low-cost spectroscopic near-infrared photodetection., Interfaces of organic donor-acceptor blends provide intermolecular charge-transfer states with red-shifted but weak absorption. By introducing an optical micro-cavity; Siegmund et al., enhance their photoresponse to achieve narrowband NIR photodetection with broad spectral tunability.

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.

The growth behavior of thin silver films on organic layers is investigated during deposition by means of simultaneous in-situ monitoring of sheet resistance and transmittance. Thermally evaporated films up to 11 nm show a distinct percolation behavior with strong resistance drop at the percolation thickness. Additionally, evaporations are divided into a sequence of one nanometer steps. In the deposition breaks, the films exhibit a ripening effect with an inversion at the percolation thickness, by changing from an increasing to decreasing sheet resistance over time. Scanning electron micrographs suggest same ripening mechanisms for islands below the percolation thickness as for holes above.

Flexible permeation barriers are a key component for flexibleorganic light emitting diodes and organic solar cells. Roll-torollprocessing is a solution to reduce the costs for barriers.However, usual web handling includes roll-layer contact.This physical contact may be critical for high quality barriers,because the barrier performance deteriorates drasticallywith the introduction of only a few defects. In this work, itis demonstrated that avoiding roll-barrier contact improvesthe barrier performance by at least a factor of 5. To minimizebarrier defects caused by substrate surface irregularities, ahigh quality substrate was used for this study. Due to the highsubstrate quality, a water vapor transmission rate (WVTR) of0.001 g/(m²d) was measured for a 37 nm thick single layerof sputtered zinc tin oxide (ZTO).

Thin film organic devices like organic solar cells require encapsulation against water vapor. Depending on the device, water vapor transmission rates (WVTR) in the range of $10^{-5}\cdot g/(m^2\cdot day)$ are needed for lifetimes of at least five years. In this work we aim at improving the encapsulation properties of opaque vacuum-evaporated aluminum back-electrodes to fulfill these barrier requirements. Water diffusion through aluminum layers is defect-driven. To reduce defect densities, the growt h behavior of the aluminum layer is modified by underlying metallic seed-layers which have shown improved performance in transparent metal thin-film electrodes. Significant improvement of WVTR can be achieved with multilayer structures. Thin interlayers that decouple the defect positions in consecutive aluminum layers provide long and tortuous diffusion-paths for water-molecules. In our study, we use the electrical calcium-test to investigate stacks of aluminum layers with various interlayers with respect to steady-state WVTR and lag-time. The interlayers consist of different planarizing, diffusion-limiting, or getter materials that absorb water-molecules as they diffuse through the barrier. These optimized aluminum multilayers are promising candidates for organic thin-film encapsulation.

Recently, bilayer resist processing combined with development in hydrofluoroether (HFE) solvents has been shown to enable single color structuring of vacuum-deposited state-of-the-art organic light-emitting diodes (OLED). In this work, we focus on further steps required to achieve multicolor structuring of p-i-n OLEDs using a bilayer resist approach. We show that the green phosphorescent OLED stack is undamaged after lift-off in HFEs, which is a necessary step in order to achieve RGB pixel array structured by means of photolithography. Furthermore, we investigate the influence of both, double resist processing on red OLEDs and exposure of the devices to ambient conditions, on the basis of the electrical, optical and lifetime parameters of the devices. Additionally, water vapor transmission rates of single and bilayer system are evaluated with thin Ca film conductance test. We conclude that diffusion of propylene glycol methyl ether acetate (PGMEA) through the fluoropolymer film is the main mechanism behind OLED degradation observed after bilayer processing.

Organic devices have to be protected with a permeation barrier against ambient moisture since their performance is strongly reduced by contact with water. The corrosion of calcium is widely used to evaluate such permeation barriers. However, design details of the calcium corrosion test may have severe consequences for the validity and precision of the measurement results. In this work, we present such a measurement distortion caused by the direct contact between calcium and the inorganic permeation barrier. Fortunately, even a 20 nm thin interlayer of a soft material (i.e., C60) sandwiched between calcium and the barrier reestablishes the validity of the measurement. In addition, we present our latest and improved electrical calcium test layout used for this investigation.

Different low-cost and flexible transparent electrode technologies, such as metal thin films (dielectric-metal-dielectric), metal nanowires (Ag and Cu), polymers and carbon nanotubes are studied and applied in small molecule-based organic solar cells and OLEDs.

We demonstrate flexible small molecular solar cells on periodically patterned plastic substrate (LCD display film) using a highly transparent poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PSS) electrode with flexible thin atomic layer deposited (ALD) AlOsubx/subtop and bottom encapsulation. The organic photovoltaic device (OPV) on this display film shows a power conversion efficiency of 7.48%, which is a 13.0% improvement as compared to a device fabricated on a planar poly-ethylen-terephtalate (PET) substrate (6.62%) and even higher than the efficiency of a device using planar glass substrate (7.15%). The improvement is mainly due to an enhanced harvesting of photons with wavelengths shorter than 500 nm. Moreover, the fully encapsulated device is sufficiently flexible to withstand a bending with a 10 mm radius for more than 50 cycles at ambient condition. These results indicate that the use of standard optical display films is a cheap, simple and efficient way to increase the photocurrent and overall efficiency of organic photovoltaic devices.

A major failure mechanism is identified in electrical calcium corrosion tests for quality assessment of high-end application moisture barriers. Accelerated calcium corrosion is found at the calcium/electrode junction, leading to an electrical bottleneck. This causes test failure not related to overall calcium loss. The likely cause is a difference in electrochemical potential between the aluminum electrodes and the calcium sensor, resulting in a corrosion element. As a solution, a thin, full-area copper layer is introduced below the calcium, shifting the corrosion element to the calcium/copper junction and inhibiting bottleneck degradation. Using the copper layer improves the level of sensitivity for the water vapor transmission rate (WVTR) by over one order of magnitude. Thin-film encapsulated samples with 20 nm of atomic layer deposited alumina barriers this way exhibit WVTRs of 6 × 10(-5) g(H2O)/m(2)/d at 38 °C, 90% relative humidity.

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 ...