The Hidden Potential of Polysilsesquioxane for High‐k: Analysis of the Origin of its Dielectric Nature and Practical Low‐Voltage‐Operating Applications beyond the Unit Device

Abstract Low‐voltage‐operating high‐performance organic field‐effect transistors (OFETs) are regarded as the building blocks of analog and digital integrated circuits for next‐generation electronics. To fulfill this, such an OFET must have high‐dielectric constant ( k ) characteristics for increasing the capacitance values to make enough of a field‐effect charge, a hydrophobic surface that does not cause charge trapping, and a low leakage current property to guarantee operating stability. This study demonstrates a new strategy to induce high‐ k characteristics (>8) with durable polysilsesquioxane (PSQ)‐based dielectrics. This strategy involves realizing a dipolar side‐chain reorientation under an electric field and its applications to low‐voltage‐driving OFETs showing high field‐effect mobility levels as high as 27 cm 2 V –1 s –1 . Different PSQs are characterized, and the differences in their characteristics lead to distinct polarization phenomena, resulting in different hysteresis behaviors during device operation. The printed unit devices can also be fabricated on flexible platforms and integrated devices through these materials and show robust switching or memory performances under low‐voltage‐operation conditions. Therefore, this facile but powerful synthesis strategy for high‐ k PSQ dielectrics can pave a new path for the production of practical printable high‐ k dielectrics for organic electronics and hence realize next‐generation integrated electronics.