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A self-assembled nanodielectric (SAND) is an ultrathin film, typically with periodic layer pairs of high-k oxide and phosphonic-acid-based π-electron (PAE) molecular layers. IPAE, having a molecular structure similar to that of PAE but with an inverted dipole direction, has recently been developed for use in thin-film transistors. Here we report that replacing PAE with IPAE in SAND-based thin-film transistors induces sizable threshold and turn-on voltage shifts, indicating the flipping of the built-in SAND polarity. The bromide counteranion (Br-) associated with the cationic stilbazolium portion of PAE or IPAE is of great importance, because its relative position strongly affects the electric dipole moment of the organic layer. Hence, a set of X-ray synchrotron measurements were designed and performed to directly measure and compare the Br- distributions within the PAE and IPAE SANDs. Two trilayer SANDs, consisting of a PAE or IPAE layer sandwiched between an HfOx and a ZrOx layer, were deposited on the SiOx surface of Si substrates or periodic Si/Mo multilayer substrates for X-ray reflectivity and X-ray standing wave measurements, respectively. Along with complementary DFT simulations, the spacings, elemental (Hf, Br, and Zr) distributions, molecular orientations, and Mulliken charge distributions of the PAE and IPAE molecules within each of the SAND trilayers were determined and correlated with the dipole inversion.

Improved understanding of fundamental structure–property relationships, particularly the effects of molecular shape and intermolecular packing on film morphology and active layer charge transport characteristics, enables more rational synthesis of new p-type small molecules. Here we investigate a series of small molecules consisting of an acene-based electron-rich core flanked by one or two electron-deficient diketopyrrolopyrrole (DPP) moieties. Through minor changes in the molecule structures, measurable variations in the crystal structure and sizable differences in macroscopic properties are achieved. The molecular symmetry as well as the conformation of the side chains affects the unit cell packing density and strength of the intermolecular electronic coupling in single crystals of all molecules in this series. The addition of a second DPP unit to the benzodithiophene (BDT) core increases molecular planarity leading to decreased reorganization energy, strong cofacial coupling, and moderate hole mobility (2.7 × 10−4 cm2 V−1 s−1). Increasing the length of the acene core from benzodithiophene to naphthodithiophene (NDT) results in a further reduction in reorganization energy and formation of smaller crystalline domains (∼11 nm) when mixed with PCBM. Decreasing the aspect ratio of the core using a “zig-zag” naphthodithiophene (zNDT) isomer results in the highest hole mobility of 1.3 × 10−3 cm2 V−1 s−1 due in part to tight lamellar (d = 13.5 A) and π–π stacking (d = 3.9 A). The hole mobility is directly correlated with the short-circuit current (11.7 mA cm−2) and solar cell efficiency (4.4%) of the highest performing zNDT:PCBM device. For each of these small molecules the calculated π-coupling constant is correlated with the hole mobility as a function of crystal structure and orientation indicating the importance of designing molecules that create extended crystalline networks with maximal π-orbital overlap.

The recent emergence of a wide variety of two-dimensional (2D) materials has created new opportunities for device concepts and applications. In particular, the availability of semiconducting transition metal dichalcogenides, in addition to semi-metallic graphene and insulating boron nitride, has enabled the fabrication of all 2D van der Waals heterostructure devices. Furthermore, the concept of van der Waals heterostructures has the potential to be significantly broadened beyond layered solids. For example, molecular and polymeric organic solids, whose surface atoms possess saturated bonds, are also known to interact via van der Waals forces and thus offer an alternative for scalable integration with 2D materials. Here, we demonstrate the integration of an organic small molecule p-type semiconductor, pentacene, with a 2D n-type semiconductor, MoS2. The resulting p-n heterojunction is gate-tunable and shows asymmetric control over the anti-ambipolar transfer characteristic. In addition, the pentacene-MoS2 heterojunction exhibits a photovoltaic effect attributable to type II band alignment, which suggests that MoS2 can function as an acceptor in hybrid solar cells., Comment: 5 figures and supporting information. To appear in Nano Letters

We compare and contrast the properties of hybrid organic-inorganic self-assembled nanodielectrics (SANDs) based on alternating layers of solution-processed ZrOxand either of two phosphonic acid-functionalized azastilbazolium Ï -units having opposite dipolar orientations. Conventional Zr-SAND and new inverted IZr-SAND are characterized by Kevin probe, optical spectroscopy, capacitance-voltage measurements, AFM, X-ray reflectivity, and electronic structure computation. The molecular dipolar orientation affects thin-film transistor (TFT) threshold and turn-on voltages for devices based on either p-channel pentacene or n-channel copper perfluorophthalocyanine. Specifically, Zr-SAND shifts the threshold and turn-on voltages to more positive values, whereas IZr-SAND shifts them in the opposite direction. Capping these SANDs with -SiMe3groups enhances the effect, affording a 1.3 V difference in turn-on voltage for IZr-SAND vs Zr-SAND-gated organic TFTs. Such tunability should facilitate the engineering of more complex circuits