Helmholtz-Zentrum Berlin für Materialien und Energie

Metal halide perovskite photovoltaic cells could potentially boost the efficiency of commercial silicon photovoltaic modules from ∼20 toward 30% when used in tandem architectures. An optimum perovskite cell optical band gap of ~1.75 electron volts (eV) can be achieved by varying halide composition, but to date, such materials have had poor photostability and thermal stability. Here we present a highly crystalline and compositionally photostable material, [HC(NH2)2](0.83)Cs(0.17)Pb(I(0.6)Br(0.4))3, with an optical band gap of ~1.74 eV, and we fabricated perovskite cells that reached open-circuit voltages of 1.2 volts and power conversion efficiency of over 17% on small areas and 14.7% on 0.715 cm(2) cells. By combining these perovskite cells with a 19%-efficient silicon cell, we demonstrated the feasibility of achieving >25%-efficient four-terminal tandem cells.

Mechanisms in Methanol Catalysis The industrial production of methanol from hydrogen and carbon monoxide depends on the use of copper and zinc oxide nanoparticles on alumina oxide supports. This catalyst is “structure sensitive”; its activity can vary by orders of magnitude, depending on how it is prepared. Behrens et al. (p. 893 , published online 19 April; see the Perspective by Greeley ) used a combination of bulk and surface-sensitive analysis and imaging methods—along with insights from density functional theory calculations—to study several catalysts, including the one similar to that used industrially. High activity depended on the presence of steps on the copper nanoparticles stabilized by defects such as stacking faults. Partial coverage of the copper nanoparticles with zinc oxide was critical for stabilizing surface intermediates such as HCO and lowering energetic barriers to the methanol product.

The efficiencies of perovskite solar cells have gone from single digits to a certified 22.1% in a few years' time. At this stage of their development, the key issues concern how to achieve further improvements in efficiency and long-term stability. We review recent developments in the quest to improve the current state of the art. Because photocurrents are near the theoretical maximum, our focus is on efforts to increase open-circuit voltage by means of improving charge-selective contacts and charge carrier lifetimes in perovskites via processes such as ion tailoring. The challenges associated with long-term perovskite solar cell device stability include the role of testing protocols, ionic movement affecting performance metrics over extended periods of time, and determination of the best ways to counteract degradation mechanisms.

Tandem solar cells that pair silicon with a metal halide perovskite are a promising option for surpassing the single-cell efficiency limit. We report a monolithic perovskite/silicon tandem with a certified power conversion efficiency of 29.15%. The perovskite absorber, with a bandgap of 1.68 electron volts, remained phase-stable under illumination through a combination of fast hole extraction and minimized nonradiative recombination at the hole-selective interface. These features were made possible by a self-assembled, methyl-substituted carbazole monolayer as the hole-selective layer in the perovskite cell. The accelerated hole extraction was linked to a low ideality factor of 1.26 and single-junction fill factors of up to 84%, while enabling a tandem open-circuit voltage of as high as 1.92 volts. In air, without encapsulation, a tandem retained 95% of its initial efficiency after 300 hours of operation.

Abstract Improving the long-term stability of perovskite solar cells is critical to the deployment of this technology. Despite the great emphasis laid on stability-related investigations, publications lack consistency in experimental procedures and parameters reported. It is therefore challenging to reproduce and compare results and thereby develop a deep understanding of degradation mechanisms. Here, we report a consensus between researchers in the field on procedures for testing perovskite solar cell stability, which are based on the International Summit on Organic Photovoltaic Stability (ISOS) protocols. We propose additional procedures to account for properties specific to PSCs such as ion redistribution under electric fields, reversible degradation and to distinguish ambient-induced degradation from other stress factors. These protocols are not intended as a replacement of the existing qualification standards, but rather they aim to unify the stability assessment and to understand failure modes. Finally, we identify key procedural information which we suggest reporting in publications to improve reproducibility and enable large data set analysis.

We present a study on the catalytic reduction of 4-nitrophenol by sodium borohydride in the presence of metal nanoparticles. The nanoparticles are embedded in spherical polyelectrolyte brushes, which consist of a polystyrene core onto which a dense layer of cationic polyelectrolyte brushes are grafted. The average size of the nanoparticles is approximately 2 nm. The kinetic data obtained by monitoring the reduction of 4-nitrophenol by UV/vis-spectroscopy could be explained in terms of the Langmuir−Hinshelwood model: The borohydride ions transfer a surface-hydrogen species in a reversible manner to the surface. Concomitantly 4-nitrophenol is adsorbed and the rate-determining step consists of the reduction of nitrophenol by the surface-hydrogen species. The apparent reaction rate can therefore be related to the total surface S of the nanoparticles, to the kinetic constant k related to the rate-determining step, and to the adsorption constants KNip and KBH4 of nitrophenol and of borohydride, respectively. In all cases, an induction time t0 was observed of the order of minutes. The reciprocal induction time can be treated as a reaction rate that is directly related to the kinetics of the surface reaction because there is a linear relation between 1/(kt0) and the concentration of nitrophenol in the solution. All data obtained for t0 so far and a comparison with data from literature indicate that the induction time is related to a slow surface reconstruction of the nanoparticles, the rate of which is directly related to the surface reaction.

Semiconductor heterostructures are the fundamental platform for many important device applications such as lasers, light-emitting diodes, solar cells, and high-electron-mobility transistors. Analogous to traditional heterostructures, layered transition metal dichalcogenide heterostructures can be designed and built by assembling individual single layers into functional multilayer structures, but in principle with atomically sharp interfaces, no interdiffusion of atoms, digitally controlled layered components, and no lattice parameter constraints. Nonetheless, the optoelectronic behavior of this new type of van der Waals (vdW) semiconductor heterostructure is unknown at the single-layer limit. Specifically, it is experimentally unknown whether the optical transitions will be spatially direct or indirect in such hetero-bilayers. Here, we investigate artificial semiconductor heterostructures built from single-layer WSe2 and MoS2. We observe a large Stokes-like shift of ∼ 100 meV between the photoluminescence peak and the lowest absorption peak that is consistent with a type II band alignment having spatially direct absorption but spatially indirect emission. Notably, the photoluminescence intensity of this spatially indirect transition is strong, suggesting strong interlayer coupling of charge carriers. This coupling at the hetero-interface can be readily tuned by inserting dielectric layers into the vdW gap, consisting of hexagonal BN. Consequently, the generic nature of this interlayer coupling provides a new degree of freedom in band engineering and is expected to yield a new family of semiconductor heterostructures having tunable optoelectronic properties with customized composite layers.

The concept that superconductivity competes with other orders in cuprate superconductors has become increasingly apparent, but obtaining direct evidence with bulk-sensitive probes is challenging. We have used resonant soft x-ray scattering to identify two-dimensional charge fluctuations with an incommensurate periodicity of ~3.2 lattice units in the copper-oxide planes of the superconductors (Y,Nd)Ba(2)Cu(3)O(6+)(x), with hole concentrations of 0.09 to 0.13 per planar Cu ion. The intensity and correlation length of the fluctuation signal increase strongly upon cooling down to the superconducting transition temperature (T(c)); further cooling below T(c) abruptly reverses the divergence of the charge correlations. In combination with earlier observations of a large gap in the spin excitation spectrum, these data indicate an incipient charge density wave instability that competes with superconductivity.

We introduce new hole-selective contacts for next-generation perovskite photovoltaics and point to design paths for molecular engineering of perfect interfaces.

Catalysis by metallic nanoparticles is certainly among the most intensely studied problems in modern nanoscience. However, reliable tests for catalytic performance of such nanoparticles are often poorly defined, which makes comparison and benchmarking rather difficult. We tackle in this tutorial review a subset of well-studied reactions that take place in aqueous phase and for which a comprehensive kinetic analysis is available. Two of these catalytic model reactions are under consideration here, namely the reduction of (i) p-nitrophenol and (ii) hexacyanoferrate (iii), both by borohydride ions. Both reactions take place at the surface of noble metal nanoparticles at room temperature and can be accurately monitored by UV-vis spectroscopy. Moreover, the total surface area of the nanoparticles in solution can be known with high precision and thus can be directly used for the kinetic analysis. Hence, these model reactions represent cases of heterogeneous catalysis that can be modelled with the accuracy typically available for homogeneous catalysis. Both model reactions allow us to discuss a number of important concepts and questions, namely the dependence of catalytic activity on the size of the nanoparticles, electrochemistry of nanoparticles, surface restructuring, the use of carrier systems and the role of diffusion control.

A fundamental understanding of the origin of oxygen evolution reaction (OER) activity of transition-metal-based electrocatalysts, especially for single precious metal atoms supported on layered double hydroxides (LDHs), is highly required for the design of efficient electrocatalysts toward further energy conversion technologies. Here, we aim toward single-atom Au supported on NiFe LDH (sAu/NiFe LDH) to clarify the activity origin of LDHs system and a 6-fold OER activity enhancement by 0.4 wt % sAu decoration. Combining with theoretical calculations, the active behavior of NiFe LDH results from the in situ generated NiFe oxyhydroxide from LDH during the OER process. With the presence of sAu, sAu/NiFe LDH possesses an overpotential of 0.21 V in contrast to the calculated result (0.18 V). We ascribe the excellent OER activity of sAu/NiFe LDH to the charge redistribution of active Fe as well as its surrounding atoms causing by the neighboring sAu on NiFe oxyhydroxide stabilized by interfacial CO32– and H2O interfacing with LDH.

We quantify recombination losses in the bulk and interfaces for different perovskite compositions and popular charge transport layers.

In response to the 2013 Update of the European Strategy for Particle Physics, the Future Circular Collider (FCC) study was launched, as an international collaboration hosted by CERN. This study covers a highest-luminosity high-energy lepton collider (FCC-ee) and an energy-frontier hadron collider (FCC-hh), which could, successively, be installed in the same 100 km tunnel. The scientific capabilities of the integrated FCC programme would serve the worldwide community throughout the 21st century. The FCC study also investigates an LHC energy upgrade, using FCC-hh technology. This document constitutes the second volume of the FCC Conceptual Design Report, devoted to the electron-positron collider FCC-ee. After summarizing the physics discovery opportunities, it presents the accelerator design, performance reach, a staged operation scenario, the underlying technologies, civil engineering, technical infrastructure, and an implementation plan. FCC-ee can be built with today's technology. Most of the FCC-ee infrastructure could be reused for FCC-hh. Combining concepts from past and present lepton colliders and adding a few novel elements, the FCC-ee design promises outstandingly high luminosity. This will make the FCC-ee a unique precision instrument to study the heaviest known particles (Z, W and H bosons and the top quark), offering great direct and indirect sensitivity to new physics.

Abstract Porous metals and metallic foams are presently the focus of very active research and development activities. There are currently around 150 institutions working on metallic foams worldwide, most of them focussing on their manufacture and characterisation. Various companies are developing and producing these materials which are now being used in numerous industrial applications such as lightweight structures, biomedical implants, filters, electrodes, catalysts, and heat exchangers. This review summarizes recent developments on these materials, with particular emphasis on research presented at the latest International Conference on Porous Metals and Metallic Foams (MetFoam 2007).

Heteroatom-doped porous carbon materials (HPCMs) have found extensive applications in adsorption/separation, organic catalysis, sensing, and energy conversion/storage. The judicious choice of carbon precursors is crucial for the manufacture of HPCMs with specific usages and maximization of their functions. In this regard, polymers as precursors have demonstrated great promise because of their versatile molecular and nanoscale structures, modulatable chemical composition, and rich processing techniques to generate textures that, in combination with proper solid-state chemistry, can be maintained throughout carbonization. This Review comprehensively surveys the progress in polymer-derived functional HPCMs in terms of how to produce and control their porosities, heteroatom doping effects, and morphologies and their related use. First, we summarize and discuss synthetic approaches, including hard and soft templating methods as well as direct synthesis strategies employing polymers to control the pores and/or heteroatoms in HPCMs. Second, we summarize the heteroatom doping effects on the thermal stability, electronic and optical properties, and surface chemistry of HPCMs. Specifically, the heteroatom doping effect, which involves both single-type heteroatom doping and codoping of two or more types of heteroatoms into the carbon network, is discussed. Considering the significance of the morphologies of HPCMs in their application spectrum, potential choices of suitable polymeric precursors and strategies to precisely regulate the morphologies of HPCMs are presented. Finally, we provide our perspective on how to predefine the structures of HPCMs by using polymers to realize their potential applications in the current fields of energy generation/conversion and environmental remediation. We believe that these analyses and deductions are valuable for a systematic understanding of polymer-derived carbon materials and will serve as a source of inspiration for the design of future HPCMs.

Materials harbouring exotic quasiparticles, such as massless Dirac and Weyl fermions, have garnered much attention from physics and material science communities due to their exceptional physical properties such as ultra-high mobility and extremely large magnetoresistances. Here, we show that the highly stable, non-toxic and earth-abundant material, ZrSiS, has an electronic band structure that hosts several Dirac cones that form a Fermi surface with a diamond-shaped line of Dirac nodes. We also show that the square Si lattice in ZrSiS is an excellent template for realizing new types of two-dimensional Dirac cones recently predicted by Young and Kane. Finally, we find that the energy range of the linearly dispersed bands is as high as 2 eV above and below the Fermi level; much larger than of other known Dirac materials. This makes ZrSiS a very promising candidate to study Dirac electrons, as well as the properties of lines of Dirac nodes.

A novel strategy for efficient growth of nitrogen-doped graphene (N-graphene) on a large scale from s-triazine molecules is presented. The growth process has been unveiled in situ using time-dependent photoemission. It has been established that a postannealing of N-graphene after gold intercalation causes a conversion of the N environment from pyridinic to graphitic, allowing to obtain more than 80% of all embedded nitrogen in graphitic form, which is essential for the electron doping in graphene. A band gap, a doping level of 300 meV, and a charge-carrier concentration of ∼8×10(12) electrons per cm2, induced by 0.4 atom % of graphitic nitrogen, have been detected by angle-resolved photoemission spectroscopy, which offers great promise for implementation of this system in next generation electronic devices.

Protein adsorption is considered to be the most important factor of the interaction between polymeric biomaterials and body fluids or tissues. Water-mediated hydrophobic and hydration forces as well as electrostatic interactions are believed to be the major factors of protein adsorption. A systematic analysis of various monolayer systems has resulted in general guidelines, the so-called "Whitesides rules". These concepts have been successfully applied for designing various protein-resistant surfaces and are being studied to expand the understanding of protein-material interactions beyond existing limitations. Theories on the mechanisms of protein adsorption are constantly being improved due to the fast-developing analytical technologies. This Review is aimed at improving these empirical guidelines with regard to present theoretical and analytical advances. Current analytical methods to test mechanistic hypotheses and theories of protein-surface interactions will be discussed. Special focus will be given to state-of-the-art bioinert and biospecific coatings and their applications in biomedicine.

Today's information society depends on our ability to controllably dope inorganic semiconductors, such as silicon, thereby tuning their electrical properties to application-specific demands. For optoelectronic devices, organic semiconductors, that is, conjugated polymers and molecules, have emerged as superior alternative owing to the ease of tuning their optical gap through chemical variability and their potential for low-cost, large-area processing on flexible substrates. There, the potential of molecular electrical doping for improving the performance of, for example, organic light-emitting devices or organic solar cells has only recently been established. The doping efficiency, however, remains conspicuously low, highlighting the fact that the underlying mechanisms of molecular doping in organic semiconductors are only little understood compared with their inorganic counterparts. Here, we review the broad range of phenomena observed upon molecularly doping organic semiconductors and identify two distinctly different scenarios: the pairwise formation of both organic semiconductor and dopant ions on one hand and the emergence of ground state charge transfer complexes between organic semiconductor and dopant through supramolecular hybridization of their respective frontier molecular orbitals on the other hand. Evidence for the occurrence of these two scenarios is subsequently discussed on the basis of the characteristic and strikingly different signatures of the individual species involved in the respective doping processes in a variety of spectroscopic techniques. The critical importance of a statistical view of doping, rather than a bimolecular picture, is then highlighted by employing numerical simulations, which reveal one of the main differences between inorganic and organic semiconductors to be their respective density of electronic states and the doping induced changes thereof. Engineering the density of states of doped organic semiconductors, the Fermi-Dirac occupation of which ultimately determines the doping efficiency, thus emerges as key challenge. As a first step, the formation of charge transfer complexes is identified as being detrimental to the doping efficiency, which suggests sterically shielding the functional core of dopant molecules as an additional design rule to complement the requirement of low ionization energies or high electron affinities in efficient n-type or p-type dopants, respectively. In an extended outlook, we finally argue that, to fully meet this challenge, an improved understanding is required of just how the admixture of dopant molecules to organic semiconductors does affect the density of states: compared with their inorganic counterparts, traps for charge carriers are omnipresent in organic semiconductors due to structural and chemical imperfections, and Coulomb attraction between ionized dopants and free charge carriers is typically stronger in organic semiconductors owing to their lower dielectric constant. Nevertheless, encouraging progress is being made toward developing a unifying picture that captures the entire range of doping induced phenomena, from ion-pair to complex formation, in both conjugated polymers and molecules. Once completed, such a picture will provide viable guidelines for synthetic and supramolecular chemistry that will enable further technological advances in organic and hybrid organic/inorganic devices.

A current drawback of spintronics is the large power that is usually required for magnetic writing, in contrast with nanoelectronics, which relies on "zero-current," gate-controlled operations. Efforts have been made to control the spin-relaxation rate, the Curie temperature, or the magnetic anisotropy with a gate voltage, but these effects are usually small and volatile. We used ferroelectric tunnel junctions with ferromagnetic electrodes to demonstrate local, large, and nonvolatile control of carrier spin polarization by electrically switching ferroelectric polarization. Our results represent a giant type of interfacial magnetoelectric coupling and suggest a low-power approach for spin-based information control.