25th Anniversary Article: Organic Photovoltaic Modules and Biopolymer Supercapacitors for Supply of Renewable Electricity: A Perspective from Africa

The role of materials in civilization is well demonstrated over the centuries and millennia, as materials have come to serve as the classifier of stages of civilization. With the advent of materials science, this relation has become even more pronounced. The pivotal role of advanced materials in industrial economies has not yet been matched by the influence of advanced materials during the transition from agricultural to modern societies. The role of advanced materials in poverty eradication can be very large, in particular if new trajectories of social and economic development become possible. This is the topic of this essay, different in format from the traditional scientific review, as we try to encompass not only two infant technologies of solar energy conversion and storage by means of organic materials, but also the social conditions for introduction of the technologies. The development of organic‐based photovoltaic energy conversion has been rapid, and promises to deliver new alternatives to well‐established silicon photovoltaics. Our recent development of organic biopolymer composite electrodes opens avenues towards the use of renewable materials in the construction of wooden batteries or supercapacitors for charge storage. Combining these new elements may give different conditions for introduction of energy technology in areas now lacking electrical grids, but having sufficient solar energy inputs. These areas are found close to the equator, and include some of the poorest regions on earth.     

25th Anniversary Article: Microstructure Dependent Bias Stability of Organic Transistors

Recent studies of the bias‐stress‐driven electrical instability of organic field‐effect transistors (OFETs) are reviewed. OFETs are operated under continuous gate and source/drain biases and these bias stresses degrade device performance. The principles underlying this bias instability are discussed, particularly the mechanisms of charge trapping. There are three main charge‐trapping sites: the semiconductor, the dielectric, and the semiconductor‐dielectric interface. The charge‐trapping phenomena in these three regions are analyzed with special attention to the microstructural dependence of bias instability. Finally, possibilities for future research in this field are presented. This critical review aims to enhance our insight into bias‐stress‐induced charge trapping in OFETs with the aim of minimizing operational instability.     

25th Anniversary Article: 25 Years of Fullerene Research in Electron Transfer Chemistry

The past 25 years have served as a test bed for exploring the chemistry and physics, in general, and the electron transfer chemistry, in particular, of low‐dimensional carbon. Nevertheless, the new realm started with the advent of fullerenes, followed in chronological order by carbon nanotubes, and, more recently, by graphene. The major thrust of this Review article is to historically recap the versatility of fullerenes regarding the design, the synthesis, and the tests as an electroactive building block in photosynthetic reaction mimics, photovoltaics, and catalysis.     

25th Anniversary Article: Engineering Hydrogels for Biofabrication

With advances in tissue engineering, the possibility of regenerating injured tissue or failing organs has become a realistic prospect for the first time in medical history. Tissue engineering – the combination of bioactive materials with cells to generate engineered constructs that functionally replace lost and/or damaged tissue – is a major strategy to achieve this goal. One facet of tissue engineering is biofabrication, where three‐dimensional tissue‐like structures composed of biomaterials and cells in a single manufacturing procedure are generated. Cell‐laden hydrogels are commonly used in biofabrication and are termed “bioinks”. Hydrogels are particularly attractive for biofabrication as they recapitulate several features of the natural extracellular matrix and allow cell encapsulation in a highly hydrated mechanically supportive three‐dimensional environment. Additionally, they allow for efficient and homogeneous cell seeding, can provide biologically‐relevant chemical and physical signals, and can be formed in various shapes and biomechanical characteristics. However, despite the progress made in modifying hydrogels for enhanced bioactivation, cell survival and tissue formation, little attention has so far been paid to optimize hydrogels for the physico‐chemical demands of the biofabrication process. The resulting lack of hydrogel bioinks have been identified as one major hurdle for a more rapid progress of the field. In this review we summarize and focus on the deposition process, the parameters and demands of hydrogels in biofabrication, with special attention to robotic dispensing as an approach that generates constructs of clinically relevant dimensions. We aim to highlight this current lack of effectual hydrogels within biofabrication and initiate new ideas and developments in the design and tailoring of hydrogels. The successful development of a “printable” hydrogel that supports cell adhesion, migration, and differentiation will significantly advance this exciting and promising approach for tissue engineering.     

25th Anniversary Article: Supramolecular Materials for Regenerative Medicine

In supramolecular materials, molecular building blocks are designed to interact with one another via non‐covalent interactions in order to create function. This offers the opportunity to create structures similar to those found in living systems that combine order and dynamics through the reversibility of intermolecular bonds. For regenerative medicine there is a great need to develop materials that signal cells effectively, deliver or bind bioactive agents in vivo at controlled rates, have highly tunable mechanical properties, but at the same time, can biodegrade safely and rapidly after fulfilling their function. These requirements make supramolecular materials a great platform to develop regenerative therapies. This review illustrates the emerging science of these materials and their use in a number of applications for regenerative medicine.     

25th Anniversary Article: Ion Exchange in Colloidal Nanocrystals

We review the progress in ion exchange in a variety of nanocrystal structures from the earliest accounts dating back over two decades ago to the present day. In recent years the number of groups using this method to form otherwise difficult or inaccessible nanoparticle shapes and morphologies has increased considerably and the field has experienced a resurgence of interest. Whilst most of the early work on cation exchange centered on II‐VI materials, the methodology has been expanded to cover a far broader range of semiconductor nanocrystals including low toxicity I‐III‐VI materials and the much less facile III‐V materials. The extent of exchange can be controlled leading to lightly doped nanoparticles, alloys, core‐shells, segmented rods and dots‐in‐rods. Progress has been driven by a better understanding of the underlying principles of the exchange process – from thermodynamic factors (differences in cation solubilities); the interactions between ions and transfer agents (solvents, ligands, anions, co‐dopants); ionic in‐diffusion mechanisms and kinetics. More recent availability of very detailed electron microscopy coupled with image reconstruction techniques has been a valuable tool to investigate the resulting heterostructures and internal interfaces. We start by surveying the range of synthetic approaches most often used to carry out ion exchange, mainly focusing on cation replacement strategies, and then describe the rich variety of nanostructures these techniques can bring forth. We also describe some of the principles that are used to establish the relative ease of exchange and to systematically improve the process where the basic energetics are less favorable. To help further the understanding of the underlying fundamentals we have gathered together useful data from the literature on solubilities, cation and anion hardness, ligand and solvent Lewis acid or base strengths for a wide range of chemical species generally used. We offer a perspective on the outlook for the field in terms of the emerging applications and the ion exchange derived materials that will enable them.     

25th Anniversary Article: Progress in Chemistry and Applications of Functional Indigos for Organic Electronics

Indigo and its derivatives are dyes and pigments with a long and distinguished history in organic chemistry. Recently, applications of this ‘old’ structure as a functional organic building block for organic electronics applications have renewed interest in these molecules and their remarkable chemical and physical properties. Natural‐origin indigos have been processed in fully bio‐compatible field effect transistors, operating with ambipolar mobilities up to 0.5 cm²/Vs and air‐stability. The synthetic derivative isoindigo has emerged as one of the most successful building‐blocks for semiconducting polymers for plastic solar cells with efficiencies > 5%. Another isomer of indigo, epindolidione, has also been shown to be one of the best reported organic transistor materials in terms of mobility (～2 cm²/Vs) and stability. This progress report aims to review very recent applications of indigoids in organic electronics, but especially to logically bridge together the hereto independent research directions on indigo, isoindigo, and other materials inspired by historical dye chemistry: a field which was the root of the development of modern chemistry in the first place.     

25th Anniversary Article: Organic Field‐Effect Transistors: The Path Beyond Amorphous Silicon

Over the past 25 years, organic field‐effect transistors (OFETs) have witnessed impressive improvements in materials performance by 3–4 orders of magnitude, and many of the key materials discoveries have been published in Advanced Materials. This includes some of the most recent demonstrations of organic field‐effect transistors with performance that clearly exceeds that of benchmark amorphous silicon‐based devices. In this article, state‐of‐the‐art in OFETs are reviewed in light of requirements for demanding future applications, in particular active‐matrix addressing for flexible organic light‐emitting diode (OLED) displays. An overview is provided over both small molecule and conjugated polymer materials for which field‐effect mobilities exceeding > 1 cm² V^–1 s^–1 have been reported. Current understanding is also reviewed of their charge transport physics that allows reaching such unexpectedly high mobilities in these weakly van der Waals bonded and structurally comparatively disordered materials with a view towards understanding the potential for further improvement in performance in the future.     

25th Anniversary Article: Dynamic Interfaces for Responsive Encapsulation Systems

Encapsulation systems are urgently needed both as micrometer and sub‐micrometer capsules for active chemicals' delivery, to encapsulate biological objects and capsules immobilized on surfaces for a wide variety of advanced applications. Methods for encapsulation, prolonged storage and controllable release are discussed in this review. Formation of stimuli responsive systems via layer‐by‐layer (LbL) assembly, as well as via mobile chemical bonding (hydrogen bonds, chemisorptions) and formation of special dynamic stoppers are presented. The most essential advances of the systems presented are multifunctionality and responsiveness to a multitude of stimuli – the possibility of formation of multi‐modal systems. Specific examples of advanced applications – drug delivery, diagnostics, tissue engineering, lab‐on‐chip and organ‐on‐chip, bio‐sensors, membranes, templates for synthesis, optical systems, and antifouling, self‐healing materials and coatings – are provided. Finally, we try to outline emerging developments.     

25th Anniversary Article: Organic Electronics Marries Photochromism: Generation of Multifunctional Interfaces,Materials, and Devices

Organic semiconductors have garnered significant interest as key components for flexible, low‐cost, and large‐area electronics. Hitherto, both materials and processing thereof seems to head towards a mature technology which shall ultimately meet expectations and efforts built up over the past years. However, by its own organic electronics cannot compete or complement the silicon‐based electronics in integrating multiple functions in a small area unless novel solutions are brought into play. Photochromic molecules are small organic molecules able to undergo reversible photochemical isomerization between (at least) two (meta)stable states which exhibit markedly different properties. They can be embedded as additional component in organic‐based materials ready to be exploited in devices such as OLEDs, OFETs, and OLETs. The structurally controlled incorporation of photochromic molecules can be done at various interfaces of a device, including the electrode/semiconductor or dielectric/semiconductor interface, or even as a binary mixture in the active layer, in order to impart a light responsive nature to the device. This can be accomplished by modulating via a light stimulus fundamental physico‐chemical properties such as charge injection and transport in the device.     

25th Anniversary Article: Designer Hydrogels for Cell Cultures: A Materials Selection Guide

Cell culturing, whether for tissue engineering or cell biology studies, always involves placing cells in a non‐natural environment and no material currently exist that can mimic the entire complexity of natural tissues and variety of cell‐matrix interactions that is found in vivo. Here, we review the vast range of hydrogels, composed of natural or synthetic polymers that provide a route to tailored microenvironments.     

25th Anniversary Article: Key Points for High‐Mobility Organic Field‐Effect Transistors

Remarkable progress has been made in developing high performance organic field‐effect transistors (OFETs) and the mobility of OFETs has been approaching the values of polycrystalline silicon, meeting the requirements of various electronic applications from electronic papers to integrated circuits. In this review, the key points for development of high mobility OFETs are highlighted from aspects of molecular engineering, process engineering and interface engineering. The importance of other factors, such as impurities and testing conditions is also addressed. Finally, the current challenges in this field for practical applications of OFETs are further discussed.     

25th Anniversary Article: MXenes: A New Family of Two‐Dimensional Materials

Recently a new, large family of two‐dimensional (2D) early transition metal carbides and carbonitrides, called MXenes, was discovered. MXenes are produced by selective etching of the A element from the MAX phases, which are metallically conductive, layered solids connected by strong metallic, ionic, and covalent bonds, such as Ti₂AlC, Ti₃AlC₂, and Ta₄AlC₃. MXenes ­combine the metallic conductivity of transition metal carbides with the hydrophilic nature of their hydroxyl or oxygen terminated surfaces. In essence, they behave as “conductive clays”. This article reviews progress—both ­experimental and theoretical—on their synthesis, structure, properties, intercalation, delamination, and potential applications. MXenes are expected to be good candidates for a host of applications. They have already shown promising performance in electrochemical energy storage systems. A detailed outlook for future research on MXenes is also presented.     

25th Anniversary Article: Interfacing Nanoparticles and Biology: New Strategies for Biomedicine

The exterior surface of nanoparticles (NPs) dictates the behavior of these systems with the outside world. Understanding the interactions of the NP surface functionality with biosystems enables the design and fabrication of effective platforms for therapeutics, diagnostics, and imaging agents. In this review, we highlight the role of chemistry in the engineering of nanomaterials, focusing on the fundamental role played by surface chemistry in controlling the interaction of NPs with proteins and cells.     

25th Anniversary Article: A Soft Future: From Robots and Sensor Skin to Energy Harvesters

Scientists are exploring elastic and soft forms of robots, electronic skin and energy harvesters, dreaming to mimic nature and to enable novel applications in wide fields, from consumer and mobile appliances to biomedical systems, sports and healthcare. All conceivable classes of materials with a wide range of mechanical, physical and chemical properties are employed, from liquids and gels to organic and inorganic solids. Functionalities never seen before are achieved. In this review we discuss soft robots which allow actuation with several degrees of freedom. We show that different actuation mechanisms lead to similar actuators, capable of complex and smooth movements in 3d space. We introduce latest research examples in sensor skin development and discuss ultraflexible electronic circuits, light emitting diodes and solar cells as examples. Additional functionalities of sensor skin, such as visual sensors inspired by animal eyes, camouflage, self‐cleaning and healing and on‐skin energy storage and generation are briefly reviewed. Finally, we discuss a paradigm change in energy harvesting, away from hard energy generators to soft ones based on dielectric elastomers. Such systems are shown to work with high energy of conversion, making them potentially interesting for harvesting mechanical energy from human gait, winds and ocean waves.     

25th Anniversary Article: Rational Design and Applications of Hydrogels in Regenerative Medicine

Hydrogels are hydrophilic polymer‐based materials with high water content and physical characteristics that resemble the native extracellular matrix. Because of their remarkable properties, hydrogel systems are used for a wide range of biomedical applications, such as three‐dimensional (3D) matrices for tissue engineering, drug‐delivery vehicles, composite biomaterials, and as injectable fillers in minimally invasive surgeries. In addition, the rational design of hydrogels with controlled physical and biological properties can be used to modulate cellular functionality and tissue morphogenesis. Here, the development of advanced hydrogels with tunable physiochemical properties is highlighted, with particular emphasis on elastomeric, light‐sensitive, composite, and shape‐memory hydrogels. Emerging technologies developed over the past decade to control hydrogel architecture are also discussed and a number of potential applications and challenges in the utilization of hydrogels in regenerative medicine are reviewed. It is anticipated that the continued development of sophisticated hydrogels will result in clinical applications that will improve patient care and quality of life.     

25th Anniversary Article: Recent Advances in n‐Type and Ambipolar Organic Field‐Effect Transistors

The advantages of organic field‐effect transistors, such as low cost, mechanical flexibility and large‐area fabrication, make them potentially useful for electronic applications such as flexible switching backplanes for video displays, radio frequency identifications and so on. A large amount of molecules were designed and synthesized for electron transporting (n‐type) and ambipolar organic semiconductors with improved performance and stability. In this review, we focus on the advances in performance and molecular design of n‐type and ambipolar semiconductors reported in the past few years.     

25th Anniversary Article: Bulk Heterojunction Solar Cells: Understanding the Mechanism of Operation

The status of understanding of the operation of bulk heterojunction (BHJ) solar cells is reviewed. Because the carrier photoexcitation recombination lengths are typically 10 nm in these disordered materials, the length scale for self‐assembly must be of order 10–20 nm. Experiments have verified the existence of the BHJ nanostructure, but the morphology remains complex and a limiting factor. Three steps are required for generation of electrical power: i) absorption of photons from the sun; ii) photoinduced charge separation and the generation of mobile carriers; iii) collection of electrons and holes at opposite electrodes. The ultrafast charge transfer process arises from fundamental quantum uncertainty; mobile carriers are directly generated (electrons in the acceptor domains and holes in the donor domains) by the ultrafast charge transfer (≈70%) with ≈30% generated by exciton diffusion to a charge separating heterojunction. Sweep‐out of the mobile carriers by the internal field prior to recombination is essential for high performance. Bimolecular recombination dominates in materials where the donor and acceptor phases are pure. Impurities degrade performance by introducing Shockly–Read–Hall decay. The review concludes with a summary of the problems to be solved to achieve the predicted power conversion efficiencies of >20% for a single cell.     

25th Anniversary Article: Hybrid Nanostructures Based on Two‐Dimensional Nanomaterials

Two‐dimensional (2D) nanomaterials, such as graphene and transition metal dichalcogenides (TMDs), receive a lot of attention, because of their intriguing properties and wide applications in catalysis, energy‐storage devices, electronics, optoelectronics, and so on. To further enhance the performance of their application, these 2D nanomaterials are hybridized with other functional nanostructures. In this review, the latest studies of 2D nanomaterial‐based hybrid nanostructures are discussed, focusing on their preparation methods, properties, and applications.