Electrical Conductivity Boost: In Situ Polypyrrole Polymerization in Monolithically Integrated Surface-Supported Metal-Organic Framework Templates.

Recent progress in synthesizing and integrating surface-supported metal-organic frameworks (SURMOFs) has highlighted their potential in developing hybrid electronic devices with exceptional mechanical flexibility, film processability, and cost-effectiveness. However, the low electrical conductivity of SURMOFs has limited their use in devices. To address this, researchers have utilized the porosity of SURMOFs to enhance electrical conductivity by incorporating conductive materials. This study introduces a method to improve the electrical conductivity of HKUST-1 templates by in situ polymerization of conductive polypyrrole (PPy) chains within the SURMOF pores (named as PPy@HKUST-1). Nanomembrane-origami technology is employed for integration, allowing a rolled-up metallic nanomembrane to contact the HKUST-1 films without causing damage. After a 24 h loading period, the electrical conductivity at room temperature reaches approximately 5.10-6 S m-1 . The nanomembrane-based contact enables reliable electrical characterization even at low temperatures. Key parameters of PPy@HKUST-1 films, such as trap barrier height, dielectric constant, and tunneling barrier height, are determined using established conduction mechanisms. These findings represent a significant advancement in real-time control of SURMOF conductivity, opening pathways for innovative electronic-optoelectronic device development. This study demonstrates the potential of SURMOFs to revolutionize hybrid electronic devices by enhancing electrical conductivity through intelligent integration strategies.

Rectification ratio and direction controlled by temperature in copper phthalocyanine ensemble molecular diodes.

Organic diodes and molecular rectifiers are fundamental electronic devices that share one common feature: current rectification ability. Since both present distinct spatial dimensions and working principles, the rectification of organic diodes is usually achieved by interface engineering, while changes in molecular structures commonly control the molecular rectifiers' features. Here, we report on the first observation of temperature-driven inversion of the rectification direction (IRD) in ensemble molecular diodes (EMDs) prepared in a vertical stack configuration. The EMDs are composed of 20 nm thick molecular ensembles of copper phthalocyanine in close contact with one of its fluorinated derivatives. The material interface was found to be responsible for modifying the junction's conduction mechanisms from nearly activationless transport to Poole-Frenkel emission and phonon-assisted tunneling. In this context, the current rectification was found to be dependent on the interplay of such distinct charge transport mechanisms. The temperature has played a crucial role in each charge transport transition, which we have investigated via electrical measurements and band diagram analysis, thus providing the fundamentals on the IRD occurrence. Our findings represent an important step towards simple and rational control of rectification in carbon-based electronic nanodevices.

Deterministic control of surface mounted metal-organic framework growth orientation on metallic and insulating surfaces.

Surface-Mounted Metal-Organic Frameworks (SURMOFs) are promising materials with a wide range of applications and increasing interest in different technological fields. The use of SURMOFs as both the active and passive tail in electronic devices is one of the most exciting possibilities for such a hybrid material. In such a context, the adhesion, roughness, and crystallinity control of SURMOF thin films are challenging and have limited their application in new functional electronic devices. Self-assembled monolayers (SAMs), which ensure the effective attachment of the SURMOF onto substrates, also play a critical role that can profoundly affect the SURMOF growth mechanism. Herein, we demonstrate that the deterministic control of the SAM chain length influences the preferential orientation of SURMOF films. As the SAM chain length increases, HKUST-1 thin films tend to change their preferential orientation from the [111] towards the [100] direction. Such control can be achieved on both electrically conducting and insulating substrates, opening the possibility of having the very same preferential crystalline orientation on surfaces of different nature, which is of fundamental importance for SURMOF-based functional electronic devices.

Nanoscale Variable-Area Electronic Devices: Contact Mechanics and Hypersensitive Pressure Application.

Nanomembranes (NMs) are freestanding structures with few-nanometer thickness and lateral dimensions up to the microscale. In nanoelectronics, NMs have been used to promote reliable electrical contacts with distinct nanomaterials, such as molecules, quantum dots, and nanowires, as well as to support the comprehension of the condensed matter down to the nanoscale. Here, we propose a tunable device architecture that is capable of deterministically changing both the contact geometry and the current injection in nanoscale electronic junctions. The device is based on a hybrid arrangement that joins metallic NMs and molecular ensembles, resulting in a versatile, mechanically compliant element. Such a feature allows the devices to accommodate a mechanical stimulus applied over the top electrodes, enlarging the junctions' active area without compromising the molecules. A model derived from the Hertzian mechanics is employed to correlate the contact dynamics with the electronic transport in these novel devices denominated as variable-area transport junctions (VATJs). As a proof of concept, we propose a direct application of the VATJs as compression gauges envisioning the development of hypersensitive pressure pixels. Regarding sensitivity (∼480 kPa-1), the VATJ-based transducers constitute a breakthrough in nanoelectronics, with the prospect of carrying its sister-field of molecular electronics out of the laboratory via integrative, hybrid organic/inorganic nanotechnology.

Tuning resistive switching on single-pulse doped multilayer memristors.

Short-period multilayers containing ultrathin atomic layers of Al embedded in titanium dioxide (TiO(2)) film-here called single-pulse doped multilayers-are fabricated by atomic layer deposition (ALD) growth methods. The approach explored here is to use Al atoms through single-pulsed deposition to locally modify the chemical environment of TiO(2) films, establishing a chemical control over the resistive switching properties of metal/oxide/metal devices. We show that this simple methodology can be employed to produce well-defined and controlled electrical characteristics on oxide thin films without compound segregation. The increase in volume of the embedded Al(2)O(3) plays a crucial role in tuning the conductance of devices, as well as the switching bias. The stacking of these oxide compounds and their use in electrical devices is investigated with respect to possible crystalline phases and local compound formation via chemical recombination. It is shown that our method can be used to produce compounds that cannot be synthesized a priori by direct ALD growth procedures but are of interest due to specific properties such as thermal or chemical stability, electrical resistivity or electric field polarization possibilities. The monolayer doping discussed here impacts considerably on the broadening of the spectrum of performance and technological applications of ALD-based memristors, allowing for additional degrees of freedom in the engineering of oxide devices.

Rolled-up nanomembranes as compact 3D architectures for field effect transistors and fluidic sensing applications.

We fabricate inorganic thin film transistors with bending radii of less than 5 µm maintaining their high electronic performance with on-off ratios of more than 10(5) and subthreshold swings of 160 mV/dec. The fabrication technology relies on the roll-up of highly strained semiconducting nanomembranes, which compacts planar transistors into three-dimensional tubular architectures opening intriguing potential for microfluidic applications. Our technique probes the ultimate limit for the bending radius of high performance thin film transistors.

Tuning giant magnetoresistance in rolled-up Co-Cu nanomembranes by strain engineering.

Compact rolled-up Co-Cu nanomembranes of high quality with different numbers of windings are realized by strain engineering. A profound analysis of magnetoresistance (MR) is performed for tubes with a single winding and a varied number of Co-Cu bilayers in the stack. Rolled-up nanomembranes with up to 12 Co-Cu bilayers are successfully fabricated by tailoring the strain state of the Cr bottom layer. By carrying out an angular dependent study, we ruled out the contribution from anisotropic MR and confirm that rolled-up Co-Cu multilayers exhibit giant magnetoresistance (GMR). No significant difference of MR is found for a single wound tube compared with planar devices. In contrast, MR in tubes with multiple windings is increased at low deposition rates of the Cr bottom layer, whereas the effect is not observable at higher rates, suggesting that interface roughness plays an important role in determining the GMR effect of the rolled-up nanomembranes. Furthermore, besides a linear increase of the MR with the number of windings, the self-rolling of nanomembranes substantially reduces the device footprint area.

High-performance organic nanomembrane based sensors for rapid in situ acid detection.

Here, we demonstrate the fabrication, characterization, and tailoring of porous organic nanomembranes and their direct integration on inorganic substrates for sensing applications. The chemically prepared nanomembranes can be integrated on both conducting and insulating substrates by either transfer or direct synthesis. We also successfully demonstrate their use for the detection of commonly used acids including HCl, H(2)SO(4), or H(3)PO(4) and their respective counterions, chlorides, sulfates, and phosphates. Impressively, the in situ acid detection is achieved down to 5 nmol·L(-1), while the quantification is feasible between 5 µmol·L(-1) and 10 mmol·L(-1). These values are among the lowest values reported so far in literature. Furthermore, the organic nanomembrane based sensor covers a wide concentration range of almost 8 orders of magnitude including the environmental limits currently adopted.

Hybrid organic/inorganic molecular heterojunctions based on strained nanomembranes.

In this work, we combine self-assembly and top-down methods to create hybrid junctions consisting of single organic molecular monolayers sandwiched between metal and/or single-crystalline semiconductor nanomembrane based electrodes. The fabrication process is fully integrative and produces a yield loss of less than 5% on-chip. The nanomembrane-based electrodes guarantee a soft yet robust contact to the molecules where the presence of pinholes and other defects becomes almost irrelevant. We also pioneer the fabrication and characterization of semiconductor/molecule/semiconductor tunneling heterojunctions which exhibit a double transition from direct tunneling to field emission and back to direct tunneling, a phenomenon which has not been reported previously.

Nanomembrane-based mesoscopic superconducting hybrid junctions.

A new method for combining top-down and bottom-up approaches to create superconductor-normal metal-superconductor niobium-based Josephson junctions is presented. Using a rolled-up semiconductor nanomembrane as scaffolding, we are able to create mesoscopic gold filament proximity junctions. These are created by electromigration of gold filaments after inducing an electric field mediated breakdown in the semiconductor nanomembrane, which can generate nanometer sized structures merely using conventional optical lithography techniques. We find that the created point contact junctions exhibit large critical currents of a few milliamps at 4.2 K and an I(c)R(n) product placing their characteristic frequency in the terahertz region. These nanometer-sized filament devices can be further optimized and integrated on a chip for their use in superconductor hybrid electronics circuits.

Relationship between chain length, disorder, and resistivity in polypyrrole films.

The effects of the polymerization temperature and of voltammetric cycling on the chain length and the resistivity of polypyrrole films are investigated. The studies provide further proof for the existence of at least two different types of polypyrrole, the so-called PPy I and PPy II. As the electropolymerization of conjugated systems in contrast to normal polymerization reactions is a fully activated process, the generation of these different types of PPy depends on experimental parameters such as temperature or formation potentials. UV-vis measurements demonstrate that PPy II comprises significantly shorter chains than PPy I (8-12 vs 32-64 units); moreover, film conductivity is found to increase with the fraction of PPy II. This fraction is changed via the polymerization temperature as well as by cyclic voltammetry, both of which can induce a metal-insulator transition. The counter-intuitive relationship between resistivity and chain length is interpreted in terms of disorder-dominated transport, in which the shorter chains of PPy II support the formation of delocalized electronic states, thereby increasing the localization length. Thus, our results are in agreement with recent broadband reflectivity measurements.