Theo J. Dingemans

A low cost azomethine-based hole transporting material for perovskite photovoltaics

Most hole transporting materials (HTMs) prepared for perovskite solar cell applications are synthesized via cross-coupling reactions that require expensive transition metal catalysts, inert reaction conditions and extensive product purification; making large-scale production cost-prohibitive. Here, we describe the synthesis of a simple azomethine-based conjugated small-molecule (EDOT-OMeTPA) which is easily prepared in a cost effective Schiff base condensation reaction, with water being the only by-product. As the hole transporter in planar CH3NH3PbI3 perovskite solar cells, efficiencies exceeding 11% were reached. This result is comparable to state-of-the-art materials such as Spiro-OMeTAD on a like-to-like comparison, while cost estimations show that the material cost is about one order of magnitude lower for EDOT-OMeTPA, resulting in a negligible cost-per-peak-Watt contribution of 0.004

All-aromatic liquid crystal triphenylamine-based poly(azomethine)s as hole transport materials for opto-electronic applications

W−1. In addition, the high synthetic accessibility of EDOT-OMeTPA also reduces the toxic chemical waste and therefore greatly reduces its environmental impact. Our results pave the way towards low-cost, environmentally friendly and efficient HTMs.

The elusive thermotropic biaxial nematic phase in rigid bent-core molecules

We have explored the opto-electronic properties of a new series of hole-transport materials based on main-chain triphenylamine-based poly(azomethine)s. 4,4′-Diaminotriphenylamine (TPA) was polymerized under benign conditions with either terephthalaldehyde (TPA-14Ta), 2,5-thiophenedicarboxaldehyde (TPA-25Th) or 1,3-isophthalaldehyde (TPA-13Iso) to yield polymers with an Mn of 5700–16 000 g mol−1. Despite the non-linear, or ‘kinked’, backbone geometry, all polymers form lyotropic solutions in chloroform and this liquid crystal (nematic) ordering could be maintained in the solid film after spin casting. All polymers exhibit high glass-transition temperatures (Tg > 250 °C) and display outstanding thermal stabilities, i.e. 5% wt loss in excess of 400 °C under nitrogen. The HOMO and LUMO energy levels of these polymers were in the range of 5.0–5.3 and 2.4–3.3 eV below the vacuum level, respectively. Introduction of a thiophene heterocycle (TPA-25Th) resulted in a material with a low optical band-gap of approximately 2.0 eV, whereas TPA-14Ta and TPA-13Iso showed optical band gaps of 2.3 and 2.6 eV, respectively. A photovoltaic device based on a TPA-25Th/PCBM blend (1 : 3) showed an EQE of 20% at 500 nm. Under simulated sunlight, the device gives an open-circuit voltage of 0.41 V, a short-circuit current of 1.23 mA cm−2 and a fill factor of 0.24, leading to a power conversion efficiency of 0.12%.

Cybotaxis dominates the nematic phase of bent-core mesogens: a small-angle diffuse X-ray diffraction study

The biaxial nematic liquid crystalline phase was predicted several decades ago. Several vigorous attempts to find it in various systems resulted in mis-identifications. The results of X-ray diffraction and optical texture studies of the phases exhibited by rigid bent-core molecules derived from 2,5-bis-(p-hydroxyphenyl)-l,3,4-oxadiazole reveal that the biaxial nematic phase is formed by three compounds of this type. X-ray diffraction studies reveal that the nematic phase of these compounds has the achiral symmetry D2h, in which the overall long axes of the molecules are oriented parallel to each other to define the major axis of the biaxial phase. The apex of the bent-cores defines the minor axis of this phase along which the planes containing the bent-cores of neighboring molecules are oriented parallel to each other.

Uniaxial and biaxial nematic liquid crystals

New temperature dependent X-ray diffraction (XRD) data on the bent-core mesogens based on the nonlinear 2,5-bis(p-hydroxyphenyl)-1,3,4-oxadiazole (ODBP) unit enable a consistent interpretation of the supramolecular structure in this class of liquid crystals. Strong evidence for cybotaxis in the high temperature phase explains the small-angle four-spot pattern and calls into question prior XRD interpretations. We find that the data can be satisfactorily explained by skewed cybotaxis, a stratified arrangement of tilted, bent-core mesogens (BCMs). We also observe the temperature-induced evolution of skewed cybotaxis to normal cybotaxis—strata wherein the long axes of the BCMs are normal to the layer fluctuations. Our XRD interpretation is compatible with the NMR data that exhibit biaxiality in the nematic phase of ODBP mesogens.

Uniaxial to biaxial nematic phase transition in a bent-core thermotropic liquid crystal by polarising microscopy

The unusual exhibition of a biaxial nematic phase in nonlinear thermotropic mesogens derived from the 2,5-oxadiazole biphenol (ODBP) core is placed in a general context; the uniaxial nematic phase of the prototypical rod-like mesogen para-quinquephenyl does not follow the classical mean-field behaviour of nematics, thus questioning the utility of such theories for quantitative predictions about biaxial nematics. The nuclear magnetic resonance spectra of labelled probe molecules dissolved in ODBP biaxial nematic phases suggest that a second critical rotation frequency, related to the differences in the transverse diamagnetic susceptibilities of the biaxial nematic, must be exceeded in order to create an aligned two-dimensional powder sample. Efforts to find higher viscosity and lower temperature biaxial nematics (with lower critical rotation rates) to confirm the above conjecture are described. Several chemical modifications of the ODBP mesogenic core are presented.

Small-molecule azomethines: Organic photovoltaics via Schiff base condensation chemistry

Polarising optical microscopy (POM) shows evidence for a reversible uniaxial nematic (NU) to biaxial nematic (NB) phase transition in a quiescent melt of bent-core mesogens (BCM). A second superimposed Schlieren texture, attributed to a second director field, grows into the NU phase on lowering the temperature and disappears again on heating, indicating a fully reversible NB to NU phase transition. This POM result together with recent X-ray data provides a new signature for the NB phase in this class of BCMs, and offers a new method for assessment of new biaxial nematic phases.

The biaxial nematic phase of oxadiazole biphenol mesogens

Conjugated small-molecule azomethines for photovoltaic applications were prepared via Schiff base condensation chemistry. Bulk heterojunction (BHJ) devices exhibit efficiencies of 1.2% with MoOx as the hole-transporting layer. The versatility and simplicity of the chemistry is illustrated by preparing a photovoltaic device directly from the reaction mixture without any form of workup.

Asymmetric oxadiazole mesogens as candidates for low-temperature biaxial nematics

Herein we review the attributes of the cluster biaxial nematic exhibited by bent-core mesogens derived from the oxadiazole biphenol mesogenic core. We present an array of static 2H NMR spectra as well as 2D powder spectra generated by rotating the nematic phase of directly labelled mesogens. Analysis of these motionally averaged NMR observations requires the nematic phase to have monoclinic symmetry. X-ray diffraction data, in particular the effects of electric and magnetic field effects, are also consonant with the cluster picture of this biaxial nematic phase.

Conjugated poly(azomethine)s via simple one-step polycondensation chemistry: synthesis, thermal and optoelectronic properties

We report the synthesis and properties of a homologous series of asymmetric, mesogenic derivatives of 2,5-bis-(p-hydroxyphenyl)-1,3,4-oxadiazole (ODBP). Benzyloxy (BnO-), alkoxy benzoate ester derivatives BnO-ODBP-Ph-O-C n , where n = 4, 5, 6, 7, 8, 9, 12, were studied by 2H-NMR, X-ray diffraction and polarising microscopy in order to ascertain if the lower temperature nematic phases exhibited biaxiality. Deuterium nuclear magnetic resonance (NMR) of labelled probes in these asymmetric mesogens does not show evidence of biaxiality. The absence of biaxiality is discussed in terms of the statistical non-linearity of these asymmetric ODBP mesogens.