Harnessing Short-Range Surface Plasmons in Planar Silver Films via Disorder-Engineered Metasurfaces.

Short-range surface plasmon polaritons (SR-SPPs) can arise due to the hybridization of surface plasmon polaritons propagating along the two interfaces of a thin metal slab. In optics, they have gained particular interest for imaging and sensing applications because of their short wavelengths at optical frequencies along with strong field enhancement. However, mediating the interaction of SR-SPPs with photons in planar films is difficult because of the large momentum mismatch. For efficient coupling, nanostructuring such thin films (∼20 nm thickness), or placing metallic nanostructures in close proximity to the planar film, is technologically challenging and can strongly influence the SR-SPP properties. In this article, harnessing SR-SPPs in planar silver films is demonstrated using disorder-engineered metasurfaces. Disorder-engineering is realized by the light-controlled growth of silver nanoparticles. The dispersion of the hybrid modes with the silver thickness is measured and compared with simulations. We anticipate these results to introduce a facile method for harnessing SR-SPPs in planar optical systems and make use of their promising properties for imaging, sensing, and nonlinear optics.

Room-Temperature Stimulated Emission and Lasing in Recrystallized Cesium Lead Bromide Perovskite Thin Films.

Cesium lead halide perovskites are of interest for light-emitting diodes and lasers. So far, thin-films of CsPbX3 have typically afforded very low photoluminescence quantum yields (PL-QY < 20%) and amplified spontaneous emission (ASE) only at cryogenic temperatures, as defect related nonradiative recombination dominated at room temperature (RT). There is a current belief that, for efficient light emission from lead halide perovskites at RT, the charge carriers/excitons need to be confined on the nanometer scale, like in CsPbX3 nanoparticles (NPs). Here, thin films of cesium lead bromide, which show a high PL-QY of 68% and low-threshold ASE at RT, are presented. As-deposited layers are recrystallized by thermal imprint, which results in continuous films (100% coverage of the substrate), composed of large crystals with micrometer lateral extension. Using these layers, the first cesium lead bromide thin-film distributed feedback and vertical cavity surface emitting lasers with ultralow threshold at RT that do not rely on the use of NPs are demonstrated. It is foreseen that these results will have a broader impact beyond perovskite lasers and will advise a revision of the paradigm that efficient light emission from CsPbX3 perovskites can only be achieved with NPs.

Spatial Atmospheric Pressure Atomic Layer Deposition of Tin Oxide as an Impermeable Electron Extraction Layer for Perovskite Solar Cells with Enhanced Thermal Stability.

Despite the notable success of hybrid halide perovskite-based solar cells, their long-term stability is still a key-issue. Aside from optimizing the photoactive perovskite, the cell design states a powerful lever to improve stability under various stress conditions. Dedicated electrically conductive diffusion barriers inside the cell stack, that counteract the ingress of moisture and prevent the migration of corrosive halogen species, can substantially improve ambient and thermal stability. Although atomic layer deposition (ALD) is excellently suited to prepare such functional layers, ALD suffers from the requirement of vacuum and only allows for a very limited throughput. Here, we demonstrate for the first time spatial ALD-grown SnOx at atmospheric pressure as impermeable electron extraction layers for perovskite solar cells. We achieve optical transmittance and electrical conductivity similar to those in SnOx grown by conventional vacuum-based ALD. A low deposition temperature of 80 °C and a high substrate speed of 2.4 m min-1 yield SnOx layers with a low water vapor transmission rate of ∼10-4 gm-2 day-1 (at 60 °C/60% RH). Thereby, in perovskite solar cells, dense hybrid Al:ZnO/SnOx electron extraction layers are created that are the key for stable cell characteristics beyond 1000 h in ambient air and over 3000 h at 60 °C. Most notably, our work of introducing spatial ALD at atmospheric pressure paves the way to the future roll-to-roll manufacturing of stable perovskite solar cells.

Light controlled assembly of silver nanoparticles.

Metal nanoparticles show a particularly strong interaction with light, which is the basis for nanoparticle plasmonics. One of the main goals of this emerging research field is the alignment of nanoparticles and their integration into sophisticated nanostructures providing a tailored interaction with light. This assembly of nanoparticles at well-controlled substrate sites often involves expensive technological approaches, such as electron beam lithography in order to fabricate the nanoparticle structures. Furthermore difficult numerical simulations are needed to predict their optical properties. Both requirements, fabrication and prediction, complicate a cost-efficient exploitation of nanoparticle plasmonics in optoelectronic devices. Here we show that silver nanoparticles deposited under exposure to visible light arrange in a way that the resulting structure shows an optimized interaction with that light. This way, the light not only controls the nanoparticle alignment with an estimated accuracy of well below 20 nm during deposition from the liquid phase, but also defines the optical properties of the growing structure, and therefore complicated prediction is not needed.

Highly sensitive gas-phase explosive detection by luminescent microporous polymer networks.

We propose microporous networks (MPNs) of a light emitting spiro-carbazole based polymer (PSpCz) as luminescent sensor for nitro-aromatic compounds. The MPNs used in this study can be easily synthesized on arbitrarily sized/shaped substrates by simple and low-cost electrochemical deposition. The resulting MPN afford an extremely high specific surface area of 1300 m(2)/g, more than three orders of magnitude higher than that of the thin films of the respective monomer. We demonstrate, that the luminescence of PSpCz is selectively quenched by nitro-aromatic analytes, e.g. nitrobenzene, 2,4-DNT and TNT. In striking contrast to a control sample based on non-porous spiro-carbazole, which does not show any luminescence quenching upon exposure to TNT at levels of 3 ppm and below, the microporous PSpCz shows a clearly detectable response even at TNT concentrations as low as 5 ppb, clearly demonstrating the advantage of microporous films as luminescent sensors for traces of explosive analytes. This level states the vapor pressure of TNT at room temperature.

Controlled Mechanical Cracking of Metal Films Deposited on Polydimethylsiloxane (PDMS).

Stretchable large area electronics conform to arbitrarily-shaped 3D surfaces and enables comfortable contact to the human skin and other biological tissue. There are approaches allowing for large area thin films to be stretched by tens of percent without cracking. The approach presented here does not prevent cracking, rather it aims to precisely control the crack positions and their orientation. For this purpose, the polydimethylsiloxane (PDMS) is hardened by exposure to ultraviolet radiation (172 nm) through an exposure mask. Only well-defined patterns are kept untreated. With these soft islands cracks at the hardened surface can be controlled in terms of starting position, direction and end position. This approach is first investigated at the hardened PDMS surface itself. It is then applied to conductive silver films deposited from the liquid phase. It is found that statistical (uncontrolled) cracking of the silver films can be avoided at strain below 35%. This enables metal interconnects to be integrated into stretchable networks. The combination of controlled cracks with wrinkling enables interconnects that are stretchable in arbitrary and changing directions. The deposition and patterning does not involve vacuum processing, photolithography, or solvents.

Highly robust transparent and conductive gas diffusion barriers based on tin oxide.

Transparent and electrically conductive gas diffusion barriers are reported. Tin oxide (SnOx ) thin films grown by atomic layer deposition afford extremely low water vapor transmission rates (WVTR) on the order of 10(-6) g (m(2) day)(-1) , six orders of magnitude better than that established with ITO layers. The electrical conductivity of SnOx remains high under damp heat conditions (85 °C/85% relative humidity (RH)), while that of ZnO quickly degrades by more than five orders of magnitude.

Facile preparation of high-performance elastically stretchable interconnects.

Sites on poly(dimethylsiloxane) are selected by ultraviolet exposure. In a subsequent electroless deposition, solid silver films are created on the selected sites only. In this way, facile vacuum-free deposition of electrodes from the liquid phase and their photoresist- and solvent-free patterning are realized. The technique enables reliable rigid-to-soft interconnects that are reversibly stretchable under arbitrary and changing stretching directions.

Polyanionic, alkylthiosulfate-based thiol precursors for conjugated polymer self-assembly onto gold and silver.

Anionic, conjugated thiophene- and fluorene-based polyelectrolytes with alkylthiosulfate side chains undergo hydrolysis under formation of alkylthiol and dialkyldisulfide functions. The hydrolysis products can be deposited onto gold or silver surfaces by self-assembly from solutions of the anionic conjugated polyelectrolyte (CPE) precursors in polar solvents such as methanol. This procedure allows solution-based surface modifications of gold and silver electrodes using environmentally friendly solvents and enables the formation of conjugated polymer bilayers. The herein presented alkylthiosulfate-substituted CPEs are promising candidates for increasing the work function of gold and silver electrodes thus improving hole injection from such electrode assemblies into organic semiconductors.

Conformal and highly luminescent monolayers of Alq3 prepared by gas-phase molecular layer deposition.

The gas-phase molecular layer deposition (MLD) of conformal and highly luminescent monolayers of tris(8-hydroxyquinolinato)aluminum (Alq3) is reported. The controlled formation of Alq3 monolayers is achieved for the first time by functionalization of the substrate with amino groups, which serve as initial docking sites for trimethyl aluminum (TMA) molecules binding datively to the amine. Thereby, upon exposure to 8-hydroxyquinoline (8-HQ), the self-limiting formation of highly luminescent Alq3 monolayers is afforded. The growth process and monolayer formation were studied and verified by in situ quartz crystal monitoring, optical emission and absorption spectroscopy, and X-ray photoelectron spectroscopy. The nature of the MLD process provides an avenue to coat arbitrarily shaped 3D surfaces and porous structures with high surface areas, as demonstrated in this work for silica aerogels. The concept presented here paves the way to highly sensitive luminescent sensors and dye-sensitized metal oxides for future applications (e.g., in photocatalysis and solar cells).

Facile encapsulation of oxide based thin film transistors by atomic layer deposition based on ozone.

A simplified encapsulation strategy for metal-oxide based TFTs, using ozone instead of water as an oxygen source in a low-temperature ALD process is demonstrated. Thereby, the threshold voltage remains unaltered and the hysteresis is permanently reduced. Costly energy- and time-consuming post-treatment processes can be avoided. This concept is widely applicable to various encapsulation materials (e.g., Al2 O3 , TiO2 , ZrO2 ) and metal-oxide channel semiconductors (e.g., zinc-tin-oxide (ZTO), indium-gallium-zinc-oxide (IGZO)).

Controlling the morphology of gold films on poly(dimethylsiloxane).

Gold films on poly(dimethylsiloxane) (PDMS) have applications in stretchable electronics, tunable diffraction gratings, soft lithography and as neural interfaces. The electrical and optical properties of these films depend critically on the morphology of the gold. Therefore, we examine qualitatively and quantitatively the factors that affect the morphology of the gold film. Three morphologies can be produced controllably: microcracked, buckled, and smooth. Which morphology a gold film will adopt depends on the film stress and the growth mode of the film. The factors that affect the film stress and growth mode, and thus the morphology, are as follows: deposition temperature, film thickness, elastic modulus, adhesion layer thickness, surface properties of the PDMS, and mechanical prestrain applied during deposition. We discuss how the different components of the film stress and growth mode of the film affect the morphology.