Adolphe Merkle Institute

Perovskite solar cells (PSCs) have now achieved efficiencies in excess of 22%, but very little is known about their long-term stability under thermal stress. So far, stability reports have hinted at the importance of substituting the organic components, but little attention has been given to the metal contact. We investigated the stability of state-of-the-art PSCs with efficiencies exceeding 20%. Remarkably, we found that exposing PSCs to a temperature of 70 °C is enough to induce gold migration through the hole-transporting layer (HTL), spiro-MeOTAD, and into the perovskite material, which in turn severely affects the device performance metrics under working conditions. Importantly, we found that the main cause of irreversible degradation is not due to decomposition of the organic and hybrid perovskite layers. By introducing a Cr metal interlayer between the HTL and gold electrode, high-temperature-induced irreversible long-term losses are avoided. This key finding is essential in the quest for achieving high efficiency, long-term stable PSCs which, in order to be commercially viable, need to withstand hard thermal stress tests.

On account of environmental concerns, the fate and adverse effects of plastics have attracted considerable interest in the past few years. Recent studies have indicated the potential for fragmentation of plastic materials into nanoparticles, i.e., "nanoplastics," and their possible accumulation in the environment. Nanoparticles can show markedly different chemical and physical properties than their bulk material form. Therefore possible risks and hazards to the environment need to be considered and addressed. However, the fate and effect of nanoplastics in the (aquatic) environment has so far been little explored. In this review, we aim to provide an overview of the literature on this emerging topic, with an emphasis on the reported impacts of nanoplastics on human health, including the challenges involved in detecting plastics in a biological environment. We first discuss the possible sources of nanoplastics and their fates and effects in the environment and then describe the possible entry routes of these particles into the human body, as well as their uptake mechanisms at the cellular level. Since the potential risks of environmental nanoplastics to humans have not yet been extensively studied, we focus on studies demonstrating cell responses induced by polystyrene nanoparticles. In particular, the influence of particle size and surface chemistry are discussed, in order to understand the possible risks of nanoplastics for humans and provide recommendations for future studies.

The latest developments in the efficiency and long-term stability of perovskite solar cells are summarized.

Nanomaterials are finding increasing use for biomedical applications such as imaging, diagnostics, and drug delivery. While it is well understood that nanoparticle (NP) physico-chemical properties can dictate biological responses and interactions, it has been difficult to outline a unifying framework to directly link NP properties to expected in vitro and in vivo outcomes. When introduced to complex biological media containing electrolytes, proteins, lipids, etc., nanoparticles (NPs) are subjected to a range of forces which determine their behavior in this environment. One aspect of NP behavior in biological systems that is often understated or overlooked is aggregation. NP aggregation will significantly alter in vitro behavior (dosimetry, NP uptake, cytotoxicity), as well as in vivo fate (pharmacokinetics, toxicity, biodistribution). Thus, understanding the factors driving NP colloidal stability and aggregation is paramount. Furthermore, studying biological interactions with NPs at the nanoscale level requires an interdisciplinary effort with a robust understanding of multiple characterization techniques. This review examines the factors that determine NP colloidal stability, the various efforts to stabilize NP in biological media, the methods to characterize NP colloidal stability in situ, and provides a discussion regarding NP interactions with cells.

Currently, perovskite solar cells (PSCs) with high performances greater than 20% contain bromine (Br), causing a suboptimal bandgap, and the thermally unstable methylammonium (MA) molecule. Avoiding Br and especially MA can therefore result in more optimal bandgaps and stable perovskites. We show that inorganic cation tuning, using rubidium and cesium, enables highly crystalline formamidinium-based perovskites without Br or MA. On a conventional, planar device architecture, using polymeric interlayers at the electron- and hole-transporting interface, we demonstrate an efficiency of 20.35% (stabilized), one of the highest for MA-free perovskites, with a drastically improved stability reached without the stabilizing influence of mesoporous interlayers. The perovskite is not heated beyond 100°C. Going MA-free is a new direction for perovskites that are inherently stable and compatible with tandems or flexible substrates, which are the main routes commercializing PSCs.

Nanoparticles (NPs) have attracted considerable attention in various fields, such as cosmetics, the food industry, material design, and nanomedicine. In particular, the fast-moving field of nanomedicine takes advantage of features of NPs for the detection and treatment of different types of cancer, fibrosis, inflammation, arthritis as well as neurodegenerative and gastrointestinal diseases. To this end, a detailed understanding of the NP uptake mechanisms by cells and intracellular localization is essential for safe and efficient therapeutic applications. In the first part of this review, we describe the several endocytic pathways involved in the internalization of NPs and we discuss the impact of the physicochemical properties of NPs on this process. In addition, the potential challenges of using various inhibitors, endocytic markers and genetic approaches to study endocytosis are addressed along with the principal (semi) quantification methods of NP uptake. The second part focuses on synthetic and bio-inspired substances, which can stimulate or decrease the cellular uptake of NPs. This approach could be interesting in nanomedicine where a high accumulation of drugs in the target cells is desirable and clearance by immune cells is to be avoided. This review contributes to an improved understanding of NP endocytic pathways and reveals potential substances, which can be used in nanomedicine to improve NP delivery.

The possibility to change the molecular assembled structures of organic and organometallic materials through mechanical stimulation is emerging as a general and powerful concept for the design of functional materials. In particular, the photophysical properties such as photoluminescence color, quantum yield, and emission lifetime of organic and organometallic fluorophores can significantly depend on the molecular packing, enabling the development of molecular materials with mechanoresponsive luminescence characteristics. Indeed, an increasing number of studies have shown in recent years that mechanical force can be utilized to change the molecular arrangement, and thereby the optical response, of luminescent molecular assemblies of π-conjugated organic or organometallic molecules. Here, the development of such mechanoresponsive luminescent (MRL) molecular assemblies consisting of organic or organometallic molecules is reviewed and emerging trends in this research field are summarized. After a brief introduction of mechanoresponsive luminescence observed in molecular assemblies, the concept of "luminescent molecular domino" is introduced, before molecular materials that show turn-on/off of photoluminescence in response to mechanical stimulation are reviewed. Mechanically stimulated multicolor changes and water-soluble MRL materials are also highlighted and approaches that combine the concept of MRL molecular assemblies with other materials types are presented in the last part of this progress report.

Low temperature planar PSCs are fabricated by SnO₂ yielding stable devices and efficiencies <italic>ca.</italic> 21%.

ABSTRACT Nanocellulose materials have undergone rapid development in recent years as promising biomedical materials because of their excellent physical and biological properties, in particular their biocompatibility, biodegradability, and low cytotoxicity. Recently, a significant amount of research has been directed toward the fabrication of advanced cellulose nanofibers with different morphologies and functional properties. These nanocellulose fibers are widely applied in medical implants, tissue engineering, drug delivery, wound‐healing, cardiovascular applications, and other medical applications. In this review, we reflect on recent advancements in the design and fabrication of advanced nanocellulose‐based biomaterials (cellulose nanocrystals, bacterial nanocellulose, and cellulose nanofibrils) that are promising for biomedical applications and discuss material requirements for each application, along with the challenges that the materials might face. Finally, we give an overview on future directions of nanocellulose‐based materials in the biomedical field. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132 , 41719.

Perovskite cells benefit from a good night's sleep.

On account of their intriguing mechanical properties, low cost, and renewable nature, high-aspect-ratio cellulose nanocrystals (CNCs) are an attractive component for many nanomaterials. Due to hydrogen bonding between their surface hydroxyl groups, unmodified CNCs (H-CNCs) aggregate easily and are often difficult to disperse. It is shown here that on account of ionic repulsion between charged surface groups, slightly phosphorylated CNCs (P-CNCs, average dimensions 31 ± 14 × 316 ± 127 nm, surface charge density = 10.8 ± 2.7 mmol/kg cellulose), prepared by controlled hydrolysis of cotton with phosphoric acid, are readily dispersible and form stable dispersions in polar solvents such as water, dimethyl sulfoxide, and dimethylformamide. Thermogravimetric analyses reveal that these P-CNCs exhibit a much higher thermal stability than partially sulfated CNCs (S-CNCs), which are frequently employed, but suffer from limited thermal stability. Nanocomposites of an ethylene oxide-epichlorohydrin copolymer and H-CNCs, S-CNCs, and P-CNCs were prepared, and their mechanical properties were studied by dynamic mechanical thermal analysis. The results show that P-CNCs offer a reinforcing capability that is comparable to that of H-CNCs or S-CNCs.

This work describes the measurement and comparison of several important properties of native cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs), such as crystallinity, morphology, aspect ratio, and surface chemistry. Measurement of the fundamental properties of seven different CNCs/CNFs, from raw material sources (bacterial, tunicate, and wood) using typical hydrolysis conditions (acid, enzymatic, mechanical, and 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-mediated oxidation), was accomplished using a variety of measurement methods. Atomic force microscopy (AFM), transmission electron microscopy (TEM), and 13C cross-polarization magic angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectroscopy were used to conclude that CNCs, which are rodlike in appearance, have a higher crystallinity than CNFs, which are fibrillar in appearance. CNC aspect ratio distributions were measured and ranged from 148±147 for tunicate-CNCs to 23±12 for wood-CNCs. Hydrophobic interactions, measured using inverse gas chromatography (IGC), were found to be an important contribution to the total surface energy of both types of cellulose. In all cases, a trace amount of naturally occurring fluorescent compounds was observed after hydrolysis. Confocal and Raman microscopy were used to confirm that the fluorescent species were unique for each cellulose source, and demonstrated that such methods can be useful for monitoring purity during CNC/CNF processing. This study reveals the broad, tunable, multidimensional material space in which CNCs and CNFs exist.

Nanotechnology has become a key word of public interest, since people realized the social and economic power of nanotechnology development. Nanotechnology has already become part of our daily life, and it will have an as yet unknown technological impact because it concerns all aspects of human life from novel building materials to electronics, cosmetics, pharmaceutics, and medicine.1 In recent years, engineered nanoparticles started to become the most important components in nanotechnology. The InternationalOrganization for Standardization (ISO) has provided specific definitions in their recent document entitled “Nanotechnologies—Terminology and definitions for nanoobjects—Nanoparticle, nanofibre and nanoplate”. As the basis of this review, the following definitions for a nanoparticle (NP) and a nano-object will be used.

Perovskite solar cells (PSCs) are currently one of the most promising photovoltaic technologies for highly efficient and cost-effective solar energy production. In only a few years, an unprecedented progression of preparation procedures and material compositions delivered lab-scale devices that have now reached record power conversion efficiencies (PCEs) higher than 20%, competing with most established solar cell materials such as silicon, CIGS, and CdTe. However, despite a large number of researchers currently involved in this topic, only a few groups in the world can reproduce >20% efficiencies on a regular n–i–p architecture. In this work, we present detailed protocols for preparing PSCs in regular (n–i–p) and inverted (p–i–n) architectures with ≥20% PCE. We aim to provide a comprehensive, reproducible description of our device fabrication protocols. We encourage the practice of reporting detailed and transparent protocols that can be more easily reproduced by other laboratories. A better reporting standard may, in turn, accelerate the development of perovskite solar cells and related research fields.

Organic-inorganic perovskites have made tremendous progress in recent years due to exceptional material properties such as high panchromatic absorption, charge carrier diffusion lengths, and a sharp optical band edge. The combination of high-quality semiconductor performance with low-cost deposition techniques seems to be a match made in heaven, creating great excitement far beyond academic ivory towers. This is particularly true for perovskite solar cells (PSCs) that have shown unprecedented gains in efficiency and stability over a time span of just five years. Now there are serious efforts for commercialization with the hope that PSCs can make a major impact in generating inexpensive, sustainable solar electricity. In this Review, we will focus on perovskite material properties as well as on devices from the atomic to the thin film level to highlight the remaining challenges and to anticipate the future developments of PSCs.

Precise knowledge regarding cellular uptake of nanoparticles is of great importance for future biomedical applications. Four different endocytotic uptake mechanisms, that is, phagocytosis, macropinocytosis, clathrin- and caveolin-mediated endocytosis, were investigated using a mouse macrophage (J774A.1) and a human alveolar epithelial type II cell line (A549). In order to deduce the involved pathway in nanoparticle uptake, selected inhibitors specific for one of the endocytotic pathways were optimized regarding concentration and incubation time in combination with fluorescently tagged marker proteins. Qualitative immunolocalization showed that J774A.1 cells highly expressed the lipid raft-related protein flotillin-1 and clathrin heavy chain, however, no caveolin-1. A549 cells expressed clathrin heavy chain and caveolin-1, but no flotillin-1 uptake-related proteins. Our data revealed an impeded uptake of 40 nm polystyrene nanoparticles by J774A.1 macrophages when actin polymerization and clathrin-coated pit formation was blocked. From this result, it is suggested that macropinocytosis and phagocytosis, as well as clathrin-mediated endocytosis, play a crucial role. The uptake of 40 nm nanoparticles in alveolar epithelial A549 cells was inhibited after depletion of cholesterol in the plasma membrane (preventing caveolin-mediated endocytosis) and inhibition of clathrin-coated vesicles (preventing clathrin-mediated endocytosis). Our data showed that a combination of several distinguishable endocytotic uptake mechanisms are involved in the uptake of 40 nm polystyrene nanoparticles in both the macrophage and epithelial cell line.

Due to their dynamic, stimuli-responsive nature, non-covalent interactions represent versatile design elements that can be found in nature in many molecular processes or materials, where adaptive behavior or reversible connectivity is required. Examples include molecular recognition processes, which trigger biological responses or cell-adhesion to surfaces, and a broad range of animal secreted adhesives with environment-dependent properties. Such advanced functionalities have inspired researchers to employ similar design approaches for the development of synthetic polymers with stimuli-responsive properties. The utilization of non-covalent interactions for the design of adhesives with advanced functionalities such as stimuli responsiveness, bonding and debonding on demand capability, surface selectivity or recyclability is a rapidly emerging subset of this field, which is summarized in this review.

Realization of the immense potential of nanomaterials for biomedical applications will require a thorough understanding of how they interact with cells, tissues, and organs. There is evidence that, depending on their physicochemical properties and subsequent interactions, nanomaterials are indeed taken up by cells. However, the subsequent release and/or intracellular degradation of the materials, transfer to other cells, and/or translocation across tissue barriers are still poorly understood. The involvement of these cellular clearance mechanisms strongly influences the long-term fate of used nanomaterials, especially if one also considers repeated exposure. Several nanomaterials, such as liposomes and iron oxide, gold, or silica nanoparticles, are already approved by the American Food and Drug Administration for clinical trials; however, there is still a huge gap of knowledge concerning their fate in the body. Herein, clinically relevant nanomaterials, their possible modes of exposure, as well as the biological barriers they must overcome to be effective are reviewed. Furthermore, the biodistribution and kinetics of nanomaterials and their modes of clearance are discussed, knowledge of the long-term fates of a selection of nanomaterials is summarized, and the critical points that must be considered for future research are addressed.

After rapid progress over the past five years, organic–inorganic perovskite solar cells (PSCs) currently exhibit photoconversion efficiencies comparable to the best commercially available photovoltaic technologies. However, instabilities in the materials and devices, primarily due to reactions with water, have kept PSCs from entering the marketplace. Here, laser beam induced current imaging is used to investigate the spatial and temporal evolution of the quantum efficiency of perovskite solar cells under controlled humidity conditions. Several interesting mechanistic aspects are revealed as the degradation proceeds along a four‐stage process. Three of the four stages can be reversed, while the fourth stage leads to irreversible decomposition of the photoactive perovskite material. A series of reactions in the PbI 2 ‐CH 3 NH 3 I‐H 2 O system explains the interplay between the interactions with water and the overall stability. Understanding of the degradation mechanisms of PSCs on a microscopic level gives insight into improving the long‐term stability.

This review gives a detailed summary and evaluation of the use of TiO2 doping to improve the performance of dye sensitized solar cells. Doping has a major effect on the band structure and trap states of TiO2, which in turn affect important properties such as the conduction band energy, charge transport, recombination and collection. The defect states of TiO2 are highly dependent on the synthesis method and thus the effect of doping may vary for different synthesis techniques, making it difficult to compare the suitability of different dopants. High-throughput methods may be employed to achieve a rough prediction on the suitability of dopants for a specific synthesis method. It was however found that nearly every employed dopant can be used to increase device performance, indicating that the improvement is not so much caused by the dopant itself, as by the defects it eliminates from TiO2. Furthermore, with the field shifting from dye sensitized solar cells to perovskite solar cells, the role doping can play to further advance this emerging field is also discussed.