Ultracompact wavefront characterization of femtosecond 3D printed microlenses using double-frequency Ronchi interferometry.

3D printed microoptics have become important tools for miniature endoscopy, novel CMOS-based on-chip sensors, OCT-fibers, among others. Until now, only image quality and spot diagrams were available for optical characterization. Here, we introduce Ronchi interferometry as ultracompact and quick quantitative analysis method for measuring the wavefront aberrations after propagating coherent light through the 3D printed miniature optics. We compare surface shapes by 3D confocal microscopy with optical characterizations by Ronchi interferograms. Phase retrieval gives us the transversal wave front aberration map, which indicates that the aberrations of our microlenses that have been printed with a Nanoscribe GT or Quantum X printer exhibit RMS wavefront aberrations as small as λ/20, Strehl ratios larger than 0.91, and near-diffraction limited modulation transfer functions. Our method will be crucial for future developments of 3D printed microoptics, as the method is ultracompact, ultra-stable, and very fast regarding measurement and evaluation. It could fit directly into a 3D printer and allows for in-situ measurements right after printing as well as fast iterations for improving the shape of the optical surface.

Anion-Exchange Membrane Water Electrolyzers.

This Review provides an overview of the emerging concepts of catalysts, membranes, and membrane electrode assemblies (MEAs) for water electrolyzers with anion-exchange membranes (AEMs), also known as zero-gap alkaline water electrolyzers. Much of the recent progress is due to improvements in materials chemistry, MEA designs, and optimized operation conditions. Research on anion-exchange polymers (AEPs) has focused on the cationic head/backbone/side-chain structures and key properties such as ionic conductivity and alkaline stability. Several approaches, such as cross-linking, microphase, and organic/inorganic composites, have been proposed to improve the anion-exchange performance and the chemical and mechanical stability of AEMs. Numerous AEMs now exceed values of 0.1 S/cm (at 60-80 °C), although the stability specifically at temperatures exceeding 60 °C needs further enhancement. The oxygen evolution reaction (OER) is still a limiting factor. An analysis of thin-layer OER data suggests that NiFe-type catalysts have the highest activity. There is debate on the active-site mechanism of the NiFe catalysts, and their long-term stability needs to be understood. Addition of Co to NiFe increases the conductivity of these catalysts. The same analysis for the hydrogen evolution reaction (HER) shows carbon-supported Pt to be dominating, although PtNi alloys and clusters of Ni(OH)2 on Pt show competitive activities. Recent advances in forming and embedding well-dispersed Ru nanoparticles on functionalized high-surface-area carbon supports show promising HER activities. However, the stability of these catalysts under actual AEMWE operating conditions needs to be proven. The field is advancing rapidly but could benefit through the adaptation of new in situ techniques, standardized evaluation protocols for AEMWE conditions, and innovative catalyst-structure designs. Nevertheless, single AEM water electrolyzer cells have been operated for several thousand hours at temperatures and current densities as high as 60 °C and 1 A/cm2, respectively.

Adjustment-free two-sided 3D direct laser writing for aligned micro-optics on both substrate sides.

3D direct laser writing is a powerful and widely used tool to create complex micro-optics. The fabrication method offers two different writing modes. During the immersion mode, an immersion medium is applied between the objective and the substrate while the photoresist is exposed on its back side. Alternatively, when using the dip-in mode, the objective is in direct contact with the photoresist and the structure is fabricated on the objective facing side of the substrate. In this Letter, we demonstrate the combination of dip-in and photoresist immersion printing, by using the photoresist itself as immersion medium. This way, two parts of a doublet objective can be fabricated on the front and back sides of a substrate, using it as a spacer with a lateral registration below 1 µm and without the need of additional alignment. This approach also enables the alignment free combination of different photoresists on the back and front sides. We use this benefit by printing a black aperture on the back of the substrate, while the objective lens is printed on the front.

Oxygen Reduction Reaction in Alkaline Media Causes Iron Leaching from Fe-N-C Electrocatalysts.

The electrochemical activity of modern Fe-N-C electrocatalysts in alkaline media is on par with that of platinum. For successful application in fuel cells (FCs), however, also high durability and longevity must be demonstrated. Currently, a limited understanding of degradation pathways, especially under operando conditions, hinders the design and synthesis of simultaneously active and stable Fe-N-C electrocatalysts. In this work, using a gas diffusion electrode half-cell coupled with inductively coupled plasma mass spectrometry setup, Fe dissolution is studied under conditions close to those in FCs, that is, with a porous catalyst layer (CL) and at current densities up to -125 mA·cm-2. Varying the rate of the oxygen reduction reaction (ORR), we show a remarkable linear correlation between the Faradaic charge passed through the electrode and the amount of Fe dissolved from the electrode. This finding is rationalized assuming that oxygen reduction and Fe dissolution reactions are interlinked, likely through a common intermediate formed during the Fe redox transitions in Fe species involved in the ORR, such as FeNxCy and Fe3C@N-C. Moreover, such a linear correlation allows the application of a simple metric─S-number─to report the material's stability. Hence, in the current work, a powerful tool for a more applied stability screening of different electrocatalysts is introduced, which allows on the one hand fast performance investigations under more realistic conditions, and on the other hand a more advanced mechanistic understanding of Fe-N-C degradation in CLs.

3D-Printed Micro Lens-in-Lens for In Vivo Multimodal Microendoscopy.

Multimodal microendoscopes enable co-located structural and molecular measurements in vivo, thus providing useful insights into the pathological changes associated with disease. However, different optical imaging modalities often have conflicting optical requirements for optimal lens design. For example, a high numerical aperture (NA) lens is needed to realize high-sensitivity fluorescence measurements. In contrast, optical coherence tomography (OCT) demands a low NA to achieve a large depth of focus. These competing requirements present a significant challenge in the design and fabrication of miniaturized imaging probes that are capable of supporting high-quality multiple modalities simultaneously. An optical design is demonstrated which uses two-photon 3D printing to create a miniaturized lens that is simultaneously optimized for these conflicting imaging modalities. The lens-in-lens design contains distinct but connected optical surfaces that separately address the needs of both fluorescence and OCT imaging within a lens of 330 µm diameter. This design shows an improvement in fluorescence sensitivity of >10x in contrast to more conventional fiber-optic design approaches. This lens-in-lens is then integrated into an intravascular catheter probe with a diameter of 520 µm. The first simultaneous intravascular OCT and fluorescence imaging of a mouse artery in vivo is reported.

Ultra-compact 3D-printed wide-angle cameras realized by multi-aperture freeform optical design.

Simultaneous realization of ultra-large field of view (FOV), large lateral image size, and a small form factor is one of the challenges in imaging lens design and fabrication. All combined this yields an extensive flow of information while conserving ease of integration where space is limited. Here, we present concepts, correction methods and realizations towards freeform multi-aperture wide-angle cameras fabricated by femtosecond direct laser writing (fsDLW). The 3D printing process gives us the design freedom to create 180° × 360° cameras with a flat form factor in the micrometer range by splitting the FOV into several apertures. Highly tilted and decentered non-rotational lens shapes as well as catadioptric elements are used in the optical design to map the FOV onto a flat surface in a Scheimpflug manner. We present methods to measure and correct freeform surfaces with up to 180° surface normals by confocal measurements, and iterative fabrication via fsDLW. Finally, approaches for digital distortion correction and image stitching are demonstrated and two realizations of freeform multi-aperture wide-angle cameras are presented.

Numerical optimization of single-mode fiber-coupled single-photon sources based on semiconductor quantum dots.

We perform extended numerical studies to maximize the overall photon coupling efficiency of fiber-coupled quantum dot single-photon sources emitting in the near-infrared and O-band and C-band. Using the finite element method, we optimize the photon extraction and fiber-coupling efficiency of quantum dot single-photon sources based on micromesas, microlenses, circular Bragg grating cavities and micropillars. The numerical simulations which consider the entire system consisting of the quantum dot source itself, the coupling lens, and the single-mode fiber, yield overall photon coupling efficiencies of up to 83%. Our work provides objectified comparability of different fiber-coupled single-photon sources and proposes optimized geometries for the realization of practical and highly efficient quantum dot single-photon sources.

Critical Advances in Ambient Air Operation of Nonaqueous Rechargeable Li-Air Batteries.

Over the past few years, great attention has been given to nonaqueous lithium-air batteries owing to their ultrahigh theoretical energy density when compared with other energy storage systems. Most of the research interest, however, is dedicated to batteries operating in pure or dry oxygen atmospheres, while Li-air batteries that operate in ambient air still face big challenges. The biggest challenges are H2 O and CO2 that exist in ambient air, which can not only form byproducts with discharge products (Li2 O2 ), but also react with the electrolyte and the Li anode. To this end, recent progress in understanding the chemical and electrochemical reactions of Li-air batteries in ambient air is critical for the development and application of true Li-air batteries. Oxygen-selective membranes, multifunctional catalysts, and electrolyte alternatives for ambient air operational Li-air batteries are presented and discussed comprehensively. In addition, separator modification and Li anode protection are covered. Furthermore, the challenges and directions for the future development of Li-air batteries are presented.

3D printed hybrid refractive/diffractive achromat and apochromat for the visible wavelength range.

Three-dimensional (3D) direct laser writing is a powerful technology to create nano- and microscopic optical devices. While the design freedom of this technology offers the possibility to reduce different monochromatic aberrations, reducing chromatic aberrations is often neglected. In this Letter, we successfully demonstrate the combination of refractive and diffractive surfaces to create a refractive/diffractive achromat and show, to the best of our knowledge, the first refractive/diffractive apochromat by using DOEs and simultaneously combining two different photoresists, namely IP-S and IP-n162. These combinations drastically reduce chromatic aberrations in 3D printed micro-optics for the visible wavelength range. The optical properties, as well as the substantial reduction of chromatic aberrations, are characterized, and we outline the benefits of 3D direct laser written achromats and apochromats for micro-optics.

Platinum Dissolution in Realistic Fuel Cell Catalyst Layers.

Pt dissolution has already been intensively studied in aqueous model systems and many mechanistic insights have been gained. Nevertheless, transfer of new knowledge to real-world fuel cell systems is still a significant challenge. To close this gap, we present a novel in situ method combining a gas diffusion electrode (GDE) half-cell with inductively coupled plasma mass spectrometry (ICP-MS). With this setup, Pt dissolution in realistic catalyst layers and the transport of dissolved Pt species through Nafion membranes were evaluated directly. We observed that 1) specific Pt dissolution increased significantly with decreasing Pt loading, 2) in comparison to experiments on aqueous model systems with flow cells, the measured dissolution in GDE experiments was considerably lower, and 3) by adding a membrane onto the catalyst layer, Pt dissolution was reduced even further. All these phenomena are attributed to the varying mass transport conditions of dissolved Pt species, influencing re-deposition and equilibrium potential.

Fabrication of a Robust PEM Water Electrolyzer Based on Non-Noble Metal Cathode Catalyst: [Mo3 S13 ]2- Clusters Anchored to N-Doped Carbon Nanotubes.

High investment costs and a dependence on noble metal catalysts currently obstruct the large-scale implementation of proton exchange membrane water electrolyzers (PEMWEs) for converting fluctuating green electricity into chemical energy via water splitting. In this context, this work presents a high-performing and stable non-noble metal catalyst for the hydrogen evolution reaction (HER), consisting of [Mo3 S13 ]2- clusters supported on nitrogen doped carbon nanotubes (NCNTs). Strikingly, a significant electrochemically induced activation of the Mo3 S13 -NCNT catalyst at high current densities is observed in full cell configuration, enabling a remarkable current density of 4 A cm-2 at a cell voltage of 2.36 V. To the authors' knowledge, this is the highest reported value to date for a PEMWE full cell using a non-noble metal HER catalyst. Furthermore, only a minor degradation of 83 µV h-1 is observed during a stability test of 100 h constant current at 1 A cm-2 , with a nearly unchanged polarization behavior after the current hold. Catalyst stability and activity are additionally analyzed via online dissolution measurements. X-ray photoelectron spectroscopy examination of the catalyst before and after electrochemical application reveals a correlation between the electrochemical activation occurring via electrodissolution with changes in the molecular structure of the Mo3 S13 -NCNT catalyst.

Distortion-free multi-element Hypergon wide-angle micro-objective obtained by femtosecond 3D printing.

In this Letter, we present a 3D-printed complex wide-angle multi-element Hypergon micro-objective, composed of aspherical lenses smaller than 1 mm, which exhibits distortion-free imaging performance. The objective is fabricated by a multi-step femtosecond two-photon lithography process. To realize the design, we apply a novel (to the best of our knowledge) approach using shadow evaporation to create highly non-transparent aperture stops, which are crucial components in many optical systems. We achieve a field-of-view (FOV) of 70°, at a resolution of 12.4 µm, and distortion-free imaging over the entire FOV. In the future, such objectives can be directly printed onto complementary metal-oxide-semiconductor (CMOS) imaging chips to produce extremely compact, high-quality image sensors to yield integrated sensor devices used in industry.

Mass-producible micro-optical elements by injection compression molding and focused ion beam structured titanium molding tools.

We demonstrate mass production compatible fabrication of polymer-based micro Fresnel lenses by injection compression molding. The extremely robust titanium-molding tool is structured with high precision by focused ion beam milling. In order to achieve optimal shape accuracy in the titanium we use an iterative design optimization. The inverse Fresnel lens structured into the titanium is transferred to polymers by injection compression molding, enabling rapid mass replication. We show that the optical performance of the molded diffractive Fresnel lenses is in good agreement with simulations, rendering our approach suitable for applications that require compact and high-quality optical elements in large numbers.

3D printed stacked diffractive microlenses.

Planar lenses such as metalenses and diffractive lenses exhibit severe field-dependent aberrations when imaging extended objects with high numerical aperture. This problem can be overcome by stacking at least two of such devices on top of each other. In this work, we present such stacked imaging systems, namely doublets and triplets of diffractive optical elements. They are fabricated by femtosecond direct laser writing in one single step without the need for alignment in sizes of below 200 µm in diameter and 100 µm in height. The lenses allow for efficient sub µm resolution imaging at visible wavelengths combined with a full field-of-view of up to 60°. As additional benefit, our approach dramatically reduces the writing times of 3D printed lens systems to below 15 minutes.

Three-dimensional direct laser written achromatic axicons and multi-component microlenses.

Femtosecond 3D printing is an important technology for manufacturing nano- and microscopic optical devices and elements. However, most structures in the past have been created using only one photoresist at a time, thus limiting potential applications. In this Letter, we successfully demonstrate the combination of two different photoresists, namely, IP-S and IP-Dip, to realize multi-component three-dimensional direct laser written optics. We use the combination of IP-S and IP-Dip to correct chromatic aberrations and to realize an achromatic axicon. In a second step, we demonstrate, to the best of our knowledge, the first three-dimensional direct laser written Fraunhofer doublet. We characterize their optical properties and measure the substantial reduction in chromatic aberrations. We outline the possibilities and benefits of creating three-dimensional direct laser written multi-component structures for micro-optics.

Alignment-free integration of apertures and nontransparent hulls into 3D-printed micro-optics.

The fabrication of 3D-printed micro-optical systems by femtosecond direct laser writing is state of the art. However, the inherent transparency of the lens mount, which is also made of photopolymer, causes a degradation of the image contrast due to stray light and scattering. Furthermore, apertures play a key role in optical design but cannot be directly integrated during 3D printing. Here, we present a superfine inkjet process for targeted filling of 3D-printed cavities in order to integrate apertures and nontransparent hulls without any alignment. Considerable contrast improvement and micro-optical systems with increased functionality are demonstrated.

Single mode fiber based delivery of OAM light by 3D direct laser writing.

We demonstrate orbital-angular momentum (OAM) light up to a topological charge of l=3 behind a single mode fiber. Femtosecond 3D direct laser writing is used to fabricate spiral phase plates of l=1,2 and 3, composed of 10 discrete steps, on the tip of single mode optical fibers. These structures efficiently convert out-coupled light from the fiber at 785 nm wavelength into optical vortex beams carrying an orbital-angular momentum of lℏper photon. Far field intensity patterns and interferograms of the OAM beams are recorded using a CCD camera. The results are in excellent agreement with numerical simulations obtained from the wave propagation method.

Ultra-compact on-chip LED collimation optics by 3D femtosecond direct laser writing.

By using two-photon lithographic 3D printing, we demonstrate additive manufacturing of a dielectric concentrator directly on a LED chip. With a size of below 200 µm in diameter and length, light output is increased by a factor of 6.2 in collimation direction, while the emission half-angle is reduced by 50%. We measure excellent form fidelity and irradiance patterns close to simulation. Additionally, a more complex shape design is presented, which exhibits a nonconventional triangular illumination pattern. The introduced method features exceptional design freedoms which can be used to tailor high-quality miniature illumination optics for specific lighting tasks, for example, endoscopy.

Allotrope-dependent activity-stability relationships of molybdenum sulfide hydrogen evolution electrocatalysts.

Molybdenum disulfide (MoS2) is widely regarded as a competitive hydrogen evolution reaction (HER) catalyst to replace platinum in proton exchange membrane water electrolysers (PEMWEs). Despite the extensive knowledge of its HER activity, stability insights under HER operation are scarce. This is paramount to ensure long-term operation of Pt-free PEMWEs, and gain full understanding on the electrocatalytically-induced processes responsible for HER active site generation. The latter are highly dependent on the MoS2 allotropic phase, and still under debate. We rigorously assess these by simultaneously monitoring Mo and S dissolution products using a dedicated scanning flow cell coupled with downstream analytics (ICP-MS), besides an electrochemical mass spectrometry setup for volatile species analysis. We observe that MoS2 stability is allotrope-dependent: lamellar-like MoS2 is highly unstable under open circuit conditions, whereas cluster-like amorphous MoS3-x instability is induced by a severe S loss during the HER and undercoordinated Mo site generation. Guidelines to operate non-noble PEMWEs are therefore provided based on the stability number metrics, and an HER mechanism which accounts for Mo and S dissolution pathways is proposed.

Applicability of Single-Layer Graphene as a Hydrogen-Blocking Interlayer in Low-Temperature PEMFCs.

Gas crossover is critical in proton exchange membrane (PEM)-based electrochemical systems. Recently, single-layer graphene (SLG) has gained great research interest due to its outstanding properties as a barrier layer for small molecules like hydrogen. However, the applicability of SLG as a gas-blocking interlayer in PEMs has yet to be fully understood. In this work, two different approaches for transferring SLG from a copper or a polymeric substrate onto PEMs are compared regarding their application in low-temperature PEM fuel cells. The SLG is sandwiched between two Nafion XL membranes to form a stable composite membrane. The successful transfer is confirmed by Raman spectroscopy and in ex situ hydrogen permeation experiments in the dry state, where a reduction of 50% upon SLG incorporation is achieved. The SLG composite membranes are characterized by their performance and hydrogen-blocking ability in a fuel cell setup at typical operating conditions of 80 °C and with fully humidified gases. The performance of the fuel cell incorporating an SLG composite membrane is equal to that of the reference cell when avoiding the direct etching process from a copper substrate, as remnants from copper etching deteriorate the performance of the fuel cell. For both transfer processes, the hydrogen crossover reduction of SLG composite membranes is only 15-19% (1.5 barabs) in the operating fuel cell. Further, hydrogen pumping experiments suggest that the barrier function of SLG impairs the water transport through the membrane, which may affect water management in electrochemical applications. In summary, this work shows the successful transfer of SLG into a PEM and confirms the effective hydrogen-blocking capability of the SLG interlayer. However, the hydrogen-blocking ability is significantly reduced when running the cell at the typical humidified operating conditions of PEM fuel cells, which follows from a combination of reversible interlayer alteration upon humidification and irreversible defect formation upon PEM fuel cell operation.