Superhigh-ε materials that exhibit exceptionally high dielectric permittivity are recognized as potential candidates for a wide range of next-generation photonic and electronic devices. In general, achieving a high-ε state requires low material symmetry, as most known high-ε materials are symmetry-broken crystals. There are few reports on fluidic high-ε dielectrics. Here, we demonstrate how small molecules with high polarity, enabled by rational molecular design and machine learning analyses, enable the development of superhigh-ε fluid materials (dielectric permittivity, ε > 10⁴) with strong second harmonic generation and macroscopic spontaneous polar ordering. The polar structures are confirmed to be identical for all the synthesized materials. Furthermore, adapting this strategy to high–molecular weight systems allows us to generalize this approach to polar polymeric materials, creating polar soft matters with spontaneous symmetry breaking.

Significance: The recent discovery of the emerging ferroelectric nematics opens an avenue not only for exploring exotic polar matter states in condensed matter physics but also for providing opportunities toward brand new liquid crystal technologies. Here, we revealed the existence of a helielectric nematic state by introducing the chirality into the ferroelectric nematics. Combining multiple intercorrelated measurements, we confirmed a helicoidal-type polar vector field in the helielectric nematics. The emergent polar symmetry triggers distinctions in topology to the dielectric cholesterics. Via proper doping of chiral generators, the helielectric state can survive down to room temperature, retaining excellent nonlinear optical and dielectric properties. Hence, it offers a stable material platform for exploring unidentified polarity–chirality–coupled textures and developing functional electrooptical devices.

Polymers with low dielectric permittivity and dielectric loss are essential for the microelectrics and wireless communication industries. The perfluorocyclobutyl (PFCB) aryl ether group has been proven to afford polymer materials with a high fluorine content and large free volume, resulting in many attractive properties, e.g., good thermal and chemical stability, high hydrophobicity, transparency and low dielectric permittivity. Herein, a series of PFCB-containing polyimides were designed and synthesized. The conformational isomers of the diamine monomer could be separated, providing an opportunity to explore the effects of the isomer conformations on the polyimide properties. All these PFCB-containing polyimides present relatively loose chain packings due to their strongly distorted chain conformations. The combined loose chain packing and high fluoro content afford these PFCB-containing polyimides excellent optical transparency and dielectric properties. In particular, dielectric permittivity and dielectric loss values as low as 2.50 and 0.0035 at high frequency (10 GHz) were obtained, enabling potential applications in the microelectronics industry.

The recently discovered ferroelectric nematic liquids incorporate to the functional combination of fluidity, processability and anisotropic optical properties of nematic liquids, an astonishing range of physical properties derived from the phase polarity. Among them, the remarkably large values of second order optical susceptibility encourage to exploit these new materials for non-linear photonic applications. Here we show that photopatterning of the alignment layer can be used to structure polarization patterns. To do so, we take advantage of the flexoelectric effect and design splay structures that geometrically define the polarization direction. We demonstrate the creation of periodic polarization structures and the possibility of guiding polarization by embedding splay structures in uniform backgrounds. The demonstrated capabilities of polarization patterning, open a promising new route for the design of ferroelectric nematic based photonic structures and their exploitation.