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Organic semiconducting small molecules have attracted increasing interest over the last decades because of their versatile, tunable optoelectronic properties and, e.g. , the ease they can be purified compared to polymeric systems. Hence, over the past few decades, a large number of small molecules, such as acenes and thiophenes, have been explored for use in semiconducting devices such as thin-film transistors. However, many of these materials can adopt various molecular arrangements, producing polymorphic structures. As a result, the same material can display vastly different optoelectronic properties. This can, in many cases, lead to a large spread of device performances. Hence, it is critical to establish knowledge- and characterization libraries towards relevant structure/processing/performance interrelations to further advance this interesting class of materials and to open new application platforms. Here, we discuss processing strategies and methodologies that allow the control and assessment of polymorph formation in semiconducting small molecules using 5,11-bis(triethylsilylethynyl)anthradithiophene (TES ADT) as a model material system. We revise how a window into the complex phase behavior of semiconducting small molecules can be obtained, how specific polymorphs can be induced, and how post-deposition treatments can be exploited. Moreover, we illustrate pathways towards patterned structures as needed to fully exploit the touted potential of this interesting class of semiconductors. 

Thermal annealing of organic semiconductors is critical for optimization of their electronic properties. The selection of the optimal annealing temperature –often done on a trial-and-error basis– is essential for achieving the most desired micro/nanostructure. While classical materials science relies on time-temperature-transformation (TTT) diagrams to predict such processing-structure relationships, this type of approach is yet to find widespread application in the field of organic electronics. In this work, we constructed a TTT diagram for crystallization of the widely studied organic semiconductor 5,11-bis(triethylsilylethynyl)anthradithiophene (TES-ADT) from its melt. Thermal analysis in the form of isothermal crystallization experiments showed distinctly different types of behaviour depending on the annealing temperature, in agreement with classical crystal nucleation and growth theory. Hence, the TTT diagram correlates with the observed variation in the number of crystal domains, the crystal coverage and film texture as well as the obtained polymorph. As a result, we are able to rationalize the influence of the annealing temperature on the charge-carrier mobility extracted from field-effect transistor (FET) measurements. Evidently, the use of TTT diagrams is a powerful tool to describe structure formation of organic semiconductors and can be used to predict processing protocols that lead to optimal device performance. 

Organic electronics technologies have attracted considerable interest over the last few decades and have become promising alternatives to conventional, inorganic platforms for specific applications. To fully exploit the touted potential of plastic electronics, however, other prerequisites than only electronic functions need to be fulfiled, including good mechanical stability, ease of processing and high device reliability. A possible method to overcome these issues is the employment of insulating:semiconducting polymer blends, which have been demonstrated to display favourable rheological and mechanical properties, generally provided by the insulating component, without negatively affecting the optoelectronic performance of the semiconductor. Here, we demonstrate that binary blends comprising the semicrystalline high-density polyethylene (HDPE) in combination with hole- and electron-transporting organic semiconductors allow fabrication of p-type and n-type thin-film transistors of notably improved device stability and, in some scenarios, improved device performance. We observe, for example, considerably lower subthreshold slopes and drastically reduced bias-stress effects in devices fabricated with a hole-transporting diketopyrrolopyrrole polymer derivative when blended with HDPE and significantly enhanced charge-carrier mobilities and shelf life in case of transistors made with blends between HDPE and the electron-transporting poly{[ N , N ′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)2,6-diyl]- alt -5,5′-(2,2′-bithiophene)}, i.e. P(NDI2OD-T2), also known as N2200, compared to the neat material, highlighting the broad, versatile benefits blending semiconducting species with a semicrystalline commodity polymer can have. 

Microfluidic cell sorters have shown great potential to revolutionize the current technique of enriching rare cells. In the past decades, different microfluidic cell sorters have been developed by researchers for separating circulating tumor cells, T-cells, and other biological markers from blood samples. However, it typically takes months or even years to design these microfluidic cell sorters by hand. Thus, researchers tend to use computer simulation (usually finite element analysis) to verify their designs before fabrication and experimental testing. Despite this, conducting precision finite element analysis of microfluidic devices is computationally expensive and labor-intensive. To address this issue, we recently presented a microfluidic simulation method that can simulate the behavior of fluids and particles in some typical microfluidic chips instantaneously. Our method decomposes the chip into channels and intersections. The behavior of fluid in each channel is determined by leveraging analogies with electronic circuits, and the behavior of fluid and particles in each intersection is determined by querying a database containing 92,934 pre-simulated channel intersections. While this approach successfully predicts the behavior of complex microfluidic chips in a fraction of the time required by existing techniques, we nonetheless identified three major limitations with this method: (1) the library of pre-simulated channel intersections is unnecessarily large (only 2,072 of 92,934 were used); (2) the library contains only cross-shaped intersections (and no other intersection geometries); and (3) the range of fluid flow rates in the library is limited to 0 to 2 cm/s. To address these deficiencies, in this work we present an improved method for instantaneously simulating the trajectories of particles in microfluidic chips. Firstly, inspired by dynamic programming, our new method optimizes the generation of pre-simulated intersection units and avoids generating unnecessary simulations. Secondly, we constructed a cloud database (http://cloud.microfluidics.cc) to share our pre-simulated results and to let users become contributors and upload their simulation results into the cloud database as a benefit to the whole microfluidic simulation community. Lastly, we investigated the impact of different channel angles and different fluid flow rates on predicting the trajectories of particles. We found a wide range of device geometries and flow rates over which our existing simulation results can be extended without having to perform additional simulations. Our method should accelerate the simulation of particles in microfluidic chips and enable researchers to design new microfluidic cell sorter chips more efficiently. 

Semiconducting mesocrystalline bulk polymer specimens that exhibit near‐intrinsic properties using channel‐die pressing are demonstrated. A predominant edge‐on orientation is obtained for poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) throughout 2 mm‐thick/wide samples. This persistent mesocrystalline arrangement at macroscopic scales allows reliable evaluation of the electronic charge‐transport anisotropy along all three crystallographic axes, with high mobilities found along the π‐stacking. Indeed, charge‐carrier mobilities of up to 2.3 cm²V⁻¹s⁻¹are measured along the π‐stack, which are some of the highest mobilities reported for polymers at low charge‐carrier densities (drop‐cast films display mobilities of maximum ≈10⁻³cm²V⁻¹s⁻¹). The structural coherence also leads to an unusually well‐defined photoluminescence line‐shape characteristic of an H‐aggregate (measured from the surface perpendicular to the materials flow), rather than the typical HJ‐aggregate feature usually found for P3HT. The approach is widely applicable: to electrical conductors and materials used in n‐type devices, such as poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} (N2200) where the mesocrystalline structure leads to high electron transport along the polymer backbones (≈1.3 cm²V⁻¹s⁻¹). This versatility and the broad applicability of channel‐die pressing signifies its promise as a straightforward, readily scalable method to fabricate bulk semiconducting polymer structures at macroscopic scales with properties typically accessible only by the tedious growth of single crystals.

 

Liquid chromophores constitute a rare but intriguing class of molecules that are in high demand for the design of luminescent inks, liquid semiconductors, and solar energy storage materials. The most common way to achieve liquid chromophores involves the introduction of long alkyl chains, which, however, significantly reduces the chromophore density. Here, strategy is presented that allows for the preparation of liquid chromophores with a minimal increase in molecular weight, using the important class of perylenes as an example. Two synergistic effects are harnessed: (1) the judicious positioning of short alkyl substituents, and (2) equimolar mixing, which in unison results in a liquid material. A series of 1‐alkyl perylene derivatives is synthesized and it is found that short ethyl or butyl chains reduce the melting temperature from 278 °C to as little as 70 °C. Then, two low‐melting derivatives are mixed, which results in materials that do not crystallize due to the increased configurational entropy of the system. As a result, liquid chromophores with the lowest reported molecular weight increase compared to the neat chromophore are obtained. The mixing strategy is readily applicable to other π‐conjugated systems and, hence, promises to yield a wide range of low molecular weight liquid chromophores.

 

Organic solar cells incorporating non‐fullerene acceptors (NFAs) have reached remarkable power conversion efficiencies of over 18%. Unlike fullerene derivatives, NFAs tend to crystallize from solutions, resulting in bulk heterojunctions that include a crystalline acceptor phase. This must be considered in any morphology‐function models. Here, it is confirmed that high‐performing solution‐processed indacenodithienothiophene‐based NFAs, i.e., ITIC and its derivatives ITIC‐M, ITIC‐2F, and ITIC‐Th, exhibit at least two crystalline forms. In addition to highly ordered polymorphs that form at high temperatures, NFAs arrange into a low‐temperature metastable phase that is readily promoted via solution processing and leads to the highest device efficiencies. Intriguingly, the low‐temperature forms seem to feature a continuous network that favors charge transport despite of a poorly order along the π–π stacking direction. As the optical absorption of the structurally more disordered low‐temperature phase can surpass that of the more ordered polymorphs while displaying comparable—or even higher—charge transport properties, it is argued that such a packing structure is an important feature for reaching highest device efficiencies, thus, providing guidelines for future materials design and crystal engineering activities.