Chemical Vapor Deposition and High-Resolution Patterning of a Highly Conductive Two-Dimensional Coordination Polymer Film.

Crystalline coordination polymers with high electrical conductivities and charge carrier mobilities might open new opportunities for electronic devices. However, current solvent-based synthesis methods hinder compatibility with microfabrication standards. Here, we describe a solvent-free chemical vapor deposition method to prepare high-quality films of the two-dimensional conjugated coordination polymer Cu-BHT (BHT = benzenehexanothiolate). This approach involves the conversion of a metal oxide precursor into Cu-BHT nanofilms with a controllable thickness (20-85 nm) and low roughness (<10 nm) through exposure to the vaporized organic linker. Moreover, the restricted metal ion mobility during the vapor-solid reaction enables high-resolution patterning via both bottom-up lithography, including the fabrication of micron-sized Hall bar and electrode patterns to accurately evaluate the conductivity and mobility values of the Cu-BHT films.

Vapor-Phase Loading of an Ionic Liquid into a Zeolitic Imidazolate Framework.

Composites formed by a metal-organic framework (MOF) and an ionic liquid (IL) are potentially interesting materials for applications ranging from gas separation to electrochemical devices. Consequently, there is a need for robust and low-cost preparation procedures that are compatible with the desired applications. We herein report a solvent-free, one-step, and vapor-based ship-in-bottle synthesis of the IL@MOF composite 1-butyl-3-methylimidazolium bromide@ZIF-8 in powder and thin film forms. In this approach, volatile IL precursors evaporate and subsequently adsorb and react within the MOF cages to form the IL.

Comparison of Thin-Film Capacitor Geometries for the Detection of Volatile Organic Compounds Using a ZIF-8 Affinity Layer.

Their chemical diversity, uniform pore sizes, and large internal surface areas make metal-organic frameworks (MOFs) highly suitable for volatile organic compound (VOC) adsorption. This work compares two geometries of capacitive VOC sensors that use the MOF material ZIF-8 as an affinity layer. When using a permeable top electrode (thickness < 25 nm), the metal-insulator-metal (MIM) sandwich configuration exhibits superior sensitivity, an improved detection limit, and a smaller footprint than the conventional interdigitated electrode layout. Moreover, the transduction of VOC adsorption in ZIF-8 via MIM capacitors is more sensitive to polar VOCs and provides better selectivity at high loadings than gravimetric and optical transductions.

Universal Limit for Air-Stable Molecular n-Doping in Organic Semiconductors.

The air sensitivity of n-doped layers is crucial for the long-term stability of organic electronic devices. Although several air-stable and highly efficient n-dopants have been developed, the reason for the varying air sensitivity between different n-doped layers, in which the n-dopant molecules are dispersed, is not fully understood. In contrast to previous studies that compared the air stability of doped films with the energy levels of neat host or dopant layers, we trace back the varying degree of air sensitivity to the energy levels of integer charge transfer states (ICTCs) formed by host anions and dopant cations. Our data indicate a universal limit for the ionization energy of ICTCs above which the n-doped semiconductors are air-stable.

Elementary steps in electrical doping of organic semiconductors.

Fermi level control by doping is established since decades in inorganic semiconductors and has been successfully introduced in organic semiconductors. Despite its commercial success in the multi-billion OLED display business, molecular doping is little understood, with its elementary steps controversially discussed and mostly-empirical-materials design. Particularly puzzling is the efficient carrier release, despite a presumably large Coulomb barrier. Here we quantitatively investigate doping as a two-step process, involving single-electron transfer from donor to acceptor molecules and subsequent dissociation of the ground-state integer-charge transfer complex (ICTC). We show that carrier release by ICTC dissociation has an activation energy of only a few tens of meV, despite a Coulomb binding of several 100 meV. We resolve this discrepancy by taking energetic disorder into account. The overall doping process is explained by an extended semiconductor model in which occupation of ICTCs causes the classically known reserve regime at device-relevant doping concentrations.

Analyzing the n-Doping Mechanism of an Air-Stable Small-Molecule Precursor.

Efficient n-doping of organic semiconductors requires electron-donating molecules with small ionization energies, making such n-dopants usually sensitive to degradation under air exposure. A workaround consists in the usage of air-stable precursor molecules containing the actual n-doping species. Here, we systematically analyze the doping mechanism of the small-molecule precursor o-MeO-DMBI-Cl, which releases a highly reducing o-MeO-DMBI radical upon thermal evaporation. n-Doping of N,N-bis(fluoren-2-yl)-naphthalene tetracarboxylic diimide yields air-stable and highly conductive films suitable for application as electron transport layer in organic solar cells. By photoelectron spectroscopy, we determine a reduced doping efficiency at high doping concentrations. We attribute this reduction to a change of the precursor decomposition mechanism with rising crucible temperature, yielding an undesired demethylation at high evaporation rates. Our results do not only show the possibility of efficient and air-stable n-doping, but also support the design of novel air-stable precursor molecules of strong n-dopants.

Publisher Correction: Elementary steps in electrical doping of organic semiconductors.

The original version of this Article contained an error in Equation 1. A factor of 'c' was included in the right-hand term. This has been corrected in the PDF and HTML versions of the Article.

Single crystal hybrid perovskite field-effect transistors.

The fields of photovoltaics, photodetection and light emission have seen tremendous activity in recent years with the advent of hybrid organic-inorganic perovskites. Yet, there have been far fewer reports of perovskite-based field-effect transistors. The lateral and interfacial transport requirements of transistors make them particularly vulnerable to surface contamination and defects rife in polycrystalline films and bulk single crystals. Here, we demonstrate a spatially-confined inverse temperature crystallization strategy which synthesizes micrometre-thin single crystals of methylammonium lead halide perovskites MAPbX3 (X = Cl, Br, I) with sub-nanometer surface roughness and very low surface contamination. These benefit the integration of MAPbX3 crystals into ambipolar transistors and yield record, room-temperature field-effect mobility up to 4.7 and 1.5 cm2 V-1 s-1 in p and n channel devices respectively, with 104 to 105 on-off ratio and low turn-on voltages. This work paves the way for integrating hybrid perovskite crystals into printed, flexible and transparent electronics.

Amorphous Tin Oxide as a Low-Temperature-Processed Electron-Transport Layer for Organic and Hybrid Perovskite Solar Cells.

Chemical bath deposition (CBD) of tin oxide (SnO2) thin films as an electron-transport layer (ETL) in a planar-heterojunction n-i-p organohalide lead perovskite and organic bulk-heterojunction (BHJ) solar cells is reported. The amorphous SnO2 (a-SnO2) films are grown from a nontoxic aqueous bath of tin chloride at a very low temperature (55 °C) and do not require postannealing treatment to work very effectively as an ETL in a planar-heterojunction n-i-p organohalide lead perovskite or organic BHJ solar cells, in lieu of the commonly used ETL materials titanium oxide (TiO2) and zinc oxide (ZnO), respectively. Ultraviolet photoelectron spectroscopy measurements on the glass/indium-tin oxide (ITO)/SnO2/methylammonium lead iodide (MAPbI3)/2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene device stack indicate that extraction of photogenerated electrons is facilitated by a perfect alignment of the conduction bands at the SnO2/MAPbI3 interface, while the deep valence band of SnO2 ensures strong hole-blocking properties. Despite exhibiting very low electron mobility, the excellent interfacial energetics combined with high transparency (Egap,optical > 4 eV) and uniform substrate coverage make the a-SnO2 ETL prepared by CBD an excellent candidate for the potentially low-cost and large-scale fabrication of organohalide lead perovskite and organic photovoltaics.

Doped organic transistors operating in the inversion and depletion regime.

The inversion field-effect transistor is the basic device of modern microelectronics and is nowadays used more than a billion times on every state-of-the-art computer chip. In the future, this rigid technology will be complemented by flexible electronics produced at extremely low cost. Organic field-effect transistors have the potential to be the basic device for flexible electronics, but still need much improvement. In particular, despite more than 20 years of research, organic inversion mode transistors have not been reported so far. Here we discuss the first realization of organic inversion transistors and the optimization of organic depletion transistors by our organic doping technology. We show that the transistor parameters--in particular, the threshold voltage and the ON/OFF ratio--can be controlled by the doping concentration and the thickness of the transistor channel. Injection of minority carriers into the doped transistor channel is achieved by doped contacts, which allows forming an inversion layer.