Semi-paracrystallinity in semi-conducting polymers.

Precise determination of structural organization of semi-conducting polymers is of paramount importance for the further development of these materials in organic electronic technologies. Yet, prior characterization of some of the best-performing materials for transistor and photovoltaic applications, which are based on polymers with rigid backbones, often resulted in conundrums in which X-ray scattering and microscopy yielded seemingly contradicting results. Here we solve the paradox by introducing a new structural model, i.e., semi-paracrystalline organization. The model establishes that the microstructure of these materials relies on a dense array of small paracrystalline domains embedded in a more disordered matrix. Thus, the overall structural order relies on two parameters: the novel concept of degree of paracrystallinity (i.e., paracrystalline volume/mass fraction, introduced here for the first time) and the lattice distortion parameter of paracrystalline domains (g-parameter from X-ray scattering). Structural parameters of the model are correlated with long-range charge carrier transport, revealing that charge transport in semi-paracrystalline materials is particularly sensitive to the interconnection of paracrystalline domains.

Physical Aging Behavior of a Glassy Polyether.

The present work aims to provide insights on recent findings indicating the presence of multiple equilibration mechanisms in physical aging of glasses. To this aim, we have investigated a glass forming polyether, poly(1-4 cyclohexane di-methanol) (PCDM), by following the evolution of the enthalpic state during physical aging by fast scanning calorimetry (FSC). The main results of our study indicate that physical aging persists at temperatures way below the glass transition temperature and, in a narrow temperature range, is characterized by a two steps evolution of the enthalpic state. Altogether, our results indicate that the simple old-standing view of physical aging as triggered by the α relaxation does not hold true when aging is carried out deep in the glassy state.

The Importance of Quantifying the Composition of the Amorphous Intermixed Phase in Organic Solar Cells.

The relation of phase morphology and solid-state microstructure with organic photovoltaic (OPV) device performance has intensely been investigated over the last twenty years. While it has been established that a combination of donor:acceptor intermixing and presence of relatively phase-pure donor and acceptor domains is needed to get an optimum compromise between charge generation and charge transport/charge extraction, a quantitative picture of how much intermixing is needed is still lacking. This is mainly due to the difficulty in quantitatively analyzing the intermixed phase, which generally is amorphous. Here, fast scanning calorimetry, which allows measurement of device-relevant thin films (<200 nm thickness), is exploited to deduce the precise composition of the intermixed phase in bulk-heterojunction structures. The power of fast scanning calorimetry is illustrated by considering two polymer:fullerene model systems. Somewhat surprisingly, it is found that a relatively small fraction (<15 wt%) of an acceptor in the intermixed amorphous phase leads to efficient charge generation. In contrast, charge transport can only be sustained in blends with a significant amount of the acceptor in the intermixed phase (in this case: ≈58 wt%). This example shows that fast scanning calorimetry is an important tool for establishing a complete compositional characterization of organic bulk heterojunctions. Hence, it will be critical in advancing quantitative morphology-function models that allow for the rational design of these devices, and in delivering insights in, for example, solar cell degradation mechanisms via phase separation, especially for more complex high-performing systems such as nonfullerene acceptor:polymer bulk heterojunctions.

Reduction of the Lattice Thermal Conductivity of Polymer Semiconductors by Molecular Doping.

Here we show that molecular doping of polymer thermoelectrics increases the electrical conductivity while reducing the thermal conductivity. A high-throughput methodology based on annealing and doping gradients within individual films is employed to self-consistently analyze and correlate electrical and thermal characteristics for the equivalent of >100 samples. We focus on the benchmark material system poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) doped with molecular acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ). The thermal conductivity of neat PBTTT films is dominated by the degree of crystallinity, with thermal percolation observed for annealing temperatures >170 °C. Upon doping the samples with a relatively low amount of F4TCNQ (anion content <1 mol %), the thermal conductivity exhibits a two-fold reduction without compromising the crystalline quality, which resembles the effect of alloy scattering observed in several inorganic systems. The analysis of the relation between thermal and electrical conductivities shows that thermal transport is dominated by a doping-induced reduced lattice contribution.

Diffusion-Limited Crystallization: A Rationale for the Thermal Stability of Non-Fullerene Solar Cells.

Organic solar cells are thought to suffer from poor thermal stability of the active layer nanostructure, a common belief that is based on the extensive work that has been carried out on fullerene-based systems. We show that a widely studied non-fullerene acceptor, the indacenodithienothiophene-based acceptor ITIC, crystallizes in a profoundly different way as compared to fullerenes. Although fullerenes are frozen below the glass-transition temperature Tg of the photovoltaic blend, ITIC can undergo a glass-crystal transition considerably below its high Tg of ∼180 °C. Nanoscopic crystallites of a low-temperature polymorph are able to form through a diffusion-limited crystallization process. The resulting fine-grained nanostructure does not evolve further with time and hence is characterized by a high degree of thermal stability. Instead, above Tg, the low temperature polymorph melts, and micrometer-sized crystals of a high-temperature polymorph develop, enabled by more rapid diffusion and hence long-range mass transport. This leads to the same detrimental decrease in photovoltaic performance that is known to occur also in the case of fullerene-based blends. Besides explaining the superior thermal stability of non-fullerene blends at relatively high temperatures, our work introduces a new rationale for the design of bulk heterojunctions that is not based on the selection of high- Tg materials per se but diffusion-limited crystallization. The planar structure of ITIC and potentially other non-fullerene acceptors readily facilitates the desired glass-crystal transition, which constitutes a significant advantage over fullerenes, and may pave the way for truly stable organic solar cells.

Conducting Polymer Scaffolds Based on Poly(3,4-ethylenedioxythiophene) and Xanthan Gum for Live-Cell Monitoring.

Conducting polymer scaffolds can promote cell growth by electrical stimulation, which is advantageous for some specific type of cells such as neurons, muscle, or cardiac cells. As an additional feature, the measure of their impedance has been demonstrated as a tool to monitor cell growth within the scaffold. In this work, we present innovative conducting polymer porous scaffolds based on poly(3,4-ethylenedioxythiophene) (PEDOT):xanthan gum instead of the well-known PEDOT:polystyrene sulfonate scaffolds. These novel scaffolds combine the conductivity of PEDOT and the mechanical support and biocompatibility provided by a polysaccharide, xanthan gum. For this purpose, first, the oxidative chemical polymerization of 3,4-ethylenedioxythiophene was carried out in the presence of polysaccharides leading to stable PEDOT:xanthan gum aqueous dispersions. Then, by a simple freeze-drying process, porous scaffolds were prepared from these dispersions. Our results indicated that the porosity of the scaffolds and mechanical properties are tuned by the solid content and formulation of the initial PEDOT:polysaccharide dispersion. Scaffolds showed interconnected pore structure with tunable sizes ranging between 10 and 150 µm and Young's moduli between 10 and 45 kPa. These scaffolds successfully support three-dimensional cell cultures of MDCK II eGFP and MDCK II LifeAct epithelial cells, achieving good cell attachment with very high degree of pore coverage. Interestingly, by measuring the impedance of the synthesized PEDOT scaffolds, the growth of the cells could be monitored.

Non-Invasive Prenatal Diagnosis in the Management of Preimplantation Genetic Diagnosis Pregnancies.

Prenatal diagnosis (PD) is recommended in pregnancies after a Preimplantation Genetic Diagnosis (PGD). However, conventional PD entails a risk of fetal loss which makes PGD patients reluctant to undergo obstetric invasive procedures. The presence of circulating fetal DNA in maternal blood allows performing a non-invasive prenatal diagnosis (NIPD) without risk for the pregnancy outcome. This work shows the introduction of NIPD for confirmation of PGD results in eight pregnancies. In those pregnancies referred to PGD for an X-linked disorder (six out of eight), fetal sex determination in maternal blood was performed to confirm fetal sex. One pregnancy referred to PGD for Marfan syndrome and one referred for Huntington disease (HD) were also analyzed. In seven out of eight cases, PGD results were confirmed by NIPD in maternal blood. No results were obtained in the HD pregnancy. NIPD in PGD pregnancies can be a reliable alternative for couples that after a long process feel reluctant to undergo PD due to the risk of pregnancy loss.

Overview of Five-Years of Experience Performing Non-Invasive Fetal Sex Assessment in Maternal Blood.

Since the discovery of the presence of fetal DNA in maternal blood, non-invasive fetal sex determination has been the test most widely translated into clinical practice. To date there is no agreement between the different laboratories performing such tests in relation to which is the best protocol. As a consequence there are almost as many protocols as laboratories offering the service, using different methodologies and thus obtaining different diagnostic accuracies. By the end of 2007, after a validation study performed in 316 maternal samples collected between the 5th and 12th week of gestation, the fetal sex determination was incorporated into clinical practice in our Service. The test is performed in the first trimester of pregnancy, and it is offered as part of the genetic counseling process for couples at risk of X-linked disorders. As a general rule and in order to avoid misdiagnosis, two samples at different gestational ages are tested per patient. The analysis is performed by the study of the SRY gene by RT-PCR. Two hundred and twenty six pregnancies have been tested so far in these 5 years. Neither false positives nor false negatives diagnoses have been registered, thus giving a diagnostic accuracy of 100%.