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The unconventional self-assembled nanodielectric (SAND) architecture is composed of solution-processed alternating inorganic (e.g., ZrOx and HfOx) and π-organic nanolayers (e.g., stilbazolium). As gate dielectrics, SANDs are compatible with a wide variety of organic and inorganic semiconductors and often impart superior thin-film transistor (TFT) performance in comparison to analogous inorganic-only dielectrics. The enhanced performance has been partly attributed to the interactions within the organic layers. To probe the role of the highly polarizable stilbazolium (Chr) organic layer in SAND structural organization and dielectric response, a saturated hydrocarbon chain-based self-assembling building block (Alk) was synthesized and incorporated in SAND structures. By using Chr and Alk in the different SAND organic layers, the effects of the Chr built-in dipole on bulk SAND structural and dielectric characteristics can be evaluated. The Zr-SAND structures are characterized by atomic force microscopy, X-ray reflectivity, metal-insulator-semiconductor electrical measurements, and pentacene-based organic TFTs. The layer identity and arrangement of the organic layers within the Zr-SAND structure are found to have a significant impact on the capacitor leakage current and pentacene transistor threshold voltage/turn-on voltage characteristics. Furthermore, significant cooperative interactions between adjacent Chr organic π-layers are important in enhancing these effects.

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.

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