Through-membrane electron-beam lithography for ultrathin membrane applications

We present a technique to fabricate ultrathin (down to 20 nm) uniform electron transparent windows at dedicated locations in a SiN membrane for in situ transmission electron microscopy experiments. An electron-beam (e-beam) resist is spray-coated on the backside of the membrane in a KOH- etched cavity in silicon which is patterned using through-membrane electron-beam lithography. This is a controlled way to make transparent windows in membranes, whilst the topside of the membrane remains undamaged and retains its flatness. Our approach was optimized for MEMS-based heating chips but can be applied to any chip design. We show two different applications of this technique for (1) fabrication of a nanogap electrode by means of electromigration in thin free-standing metal films and (2) making low-noise graphene nanopore devices

Electrical detection of spin state switching in electromigrated nanogap devices

Spin crossover is an effect shown in some transition metal complexes where the spin state of the molecule undergoes a transition from a low spin to a high spin state via the application of light, pressure or a change in temperature. This behaviour makes these complexes an attractive candidate to form electronic molecular-scale switches as the electrical resistance of the compound differs between the two spin states. Although the spin crossover effect is commonly studied in its bulk form, the integration of a single molecule into a solid-state device while maintaining the magnetic bi-stability is highly desirable, but remains challenging. This is not only due to difficulties in capturing a single molecule between electrodes and making electrical connections but it is also due to the strong coupling effects imparted on the molecule by the high-density metallic states of the electrodes that can prevent the spin transition from occurring.In recent years there have been many attempts at studying spin crossover complexes at a single molecule level. Many of these have used scanning tunneling microscopy or break junction techniques. While these studies have highlighted the unique and promising electronic properties of these compounds, these techniques are unsuitable for real world devices. This thesis demonstrates a means to make electrical contact to single or small numbers of molecules between gold electrodes fabricated using a bilayer nanoimprint lithography and a feedback controlled electromigration method. This method, enabling high throughput and low-cost fabrication is potentially suitable for scaling to large area planar devices and as such may be used for commercially producing molecular devices.To validate the quality of the nanogaps, devices containing self-assembled monolayers of benzenethiol were first studied. The shape and magnitude of I-V curves measured on nanogap devices containing the benzenethiol monolayers are in good agreement with previously published work using similar molecules in mechanically controlled break junctions. The resulting I-V characteristics were analyzed using the single level resonant tunneling model as well as transition voltage spectroscopy and are consistent with transport through molecular junctions in which the benzenethiol molecules are - stacked. These highly conducting molecular junctions may have potential uses for “soft” coupling to sensitive target molecules.Following validation of the molecular nanojunction fabrication and measurement process, the experimental work shifted to studying electronic transport through spin crossover complexes with a focus on Schiff-base compounds that are specifically tailored for surface deposition. In the case of measurements made on the bulk compound, a sharp spin transition centered at a temperature around 80 K was observed, while a shift to lower temperatures was found for thin films of the complex. In contrast, nanojunction devices containing single molecules displayed very different behaviour, with distinct and reproducible telegraphic-like switching between two resistance states when cooled below 160 K. These two states are attributed to the two different spin states of the complex. The presence of these two resistive states indicates that the spin crossover is preserved at the single molecule level and that a spin-state dependent tunneling process is taking place. Interestingly, in some cases a multi-level switching behaviour is detected with four possible conductance states. This behaviour is attributed to the presence of two spin crossover molecules in the nanogap

Nanogap Device: Fabrication and Applications

A nanogap device as a platform for nanoscale electronic devices is presented. Integrated nanostructures on the platform have been used to functionalize the nanogap for biosensor and molecular electronics. Nanogap devices have great potential as a tool for investigating physical phenomena at the nanoscale in nanotechnology. In this dissertation, a laterally self-aligned nanogap device is presented and its feasibility is demonstrated with a nano ZnO dot light emitting diode (LED) and the growth of a metallic sharp tip forming a subnanometer gap suitable for single molecule attachment. For realizing a nanoscale device, a resolution of patterning is critical, and many studies have been performed to overcome this limitation. The creation of a sub nanoscale device is still a challenge. To surmount the challenge, novel processes including double layer etch mask and crystallographic axis alignment have been developed. The processes provide an effective way for making a suspended nanogap device consisting of two self-aligned sharp tips with conventional lithography and 3-D micromachining using anisotropic wet chemical Si etching. As conventional lithography is employed, the nanogap device is fabricated in a wafer scale and the processes assure the productivity and the repeatability. The anisotropic Si etching determines a final size of the nanogap, which is independent of the critical dimension of the lithography used. A nanoscale light emitting device is investigated. A nano ZnO dot is directly integrated on a silicon nanogap device by Zn thermal oxidation followed by Ni and Zn blanket evaporation instead of complex and time consuming processes for integrating nanostructure. The electrical properties of the fabricated LED device are analyzed for its current-voltage characteristic and metal-semiconductor-metal model. Furthermore, the electroluminescence spectrum of the emitted light is measured with a monochromator implemented with a CCD camera to understand the optical properties. The atomically sharp metallic tips are grown by metal ion migration induced by high electric field across a nanogap. To investigate the growth mechanism, in-situ TEM is conducted and the growing is monitored. The grown dendrite nanostructures show less than 1nm curvature of radius. These nanostructures may be compatible for studying the electrical properties of single molecule

Nanogaps with very large aspect ratios for electrical measurements

For nanoscale electrical characterization and device fabrication it is often desirable to fabricate planar metal electrodes separated by large aspect ratio gaps with interelectrode distances well below 100 nm. We demonstrate a self-aligned process to accomplish this goal using a thin Cr film as a sacrificial etch layer. The resulting gaps can be as small as 10 nm and have aspect ratios exceeding 1000, with excellent interelectrode isolation. Such Ti/Au electrodes are demonstrated on Si substrates and are used to examine a voltage-driven transition in magnetite nanostructures. This shows the utility of this fabrication approach even with relatively reactive substrates.Comment: 4 pages, 4 figure

Nanoscale junctions for single molecule electronics fabricated using bilayer nanoimprint lithography combined with feedback controlled electromigration

Nanoimprint lithography (NIL) is a fast, simple and high throughput technique that allows fabrication of structures with nanometre precision features at low cost. We present an advanced bilayer nanoimprint lithography approach to fabricate four terminal nanojunction devices for use in single molecule electronic studies. In the first part of this work, we demonstrate a NIL lift-off process using a bilayer resist technique that negates problems associated with metal side-wall tearing during lift-off. In addition to precise nanoscale feature replication, we show that it is possible to imprint micron-sized features while still maintaining a bilayer structure enabling an undercut resist structure to be formed. This is accomplished by choosing suitable imprint parameters as well as residual layer etching depth and development time. We then use a feedback controlled electromigration procedure, to produce room-temperature stable nanogap electrodes with sizes below 2 nm. This approach facilitates the integration of molecules in stable, solid-state molecular electronic devices as demonstrated by incorporating benzenethiol as molecular bridges between the electrodes and characterizing its electronics properties through current-voltage measurements. The observation of molecular transport signatures, showing current suppression in the I-V behaviour at low voltage, which is then lifted at high voltage, signifying on- and off-resonant transport through molecular levels as a function of voltage, is confirmed in repeated I-V sweeps. The large conductance, symmetry of the I-V sweep and small value of the voltage minimum in transition voltage spectroscopy indicates the bridging of the two benzenethiol molecules is by π-stacking

Development Of An Efficient Molecular Single-electron Transport Spectroscopy

In this thesis I present a complete and detailed guide for the development process and fabrication of efficient single-electron transistors (SETs) and a better single-molecule magnets (SMMs) deposition yield. Starting from a commercial Si/SiO2 wafer I show the steps for the deposition of different layers to fabricate a SET as well as the improvements achieved in those for a completely functional SET device. The development process is based on a combination of optical lithography and e-beam lithography with metal deposition in ultra-high vacuum. The improvements involve a better conductance in the Al gate component, with a controlled formation of the superficial oxide layer and a faster feedback electromigration-induced breaking of Au nanowires for the creation of nanogaps at room temperature. The gate component is improved by increasing its thickness and exposing it to plasma oxidation for the complete oxidation of its surface. The nanowire breaking is realized at room temperature to make use of the surface tension of Au, which, after a previous feedback procedure, eventually opens the final gap in the nanowire. Finally, I demonstrate a new technique that allows increasing the yield of having a SMM connected in the nanowire gap. This new technique is based on monitoring the resistance of the broken nanowires during the SMM deposition from a controlled liquid solution at room temperature. When the resistance ( \u3e GΩ for open gaps) drops to values below Mega-ohms (characteristic resistance of a molecule bridging the gap) for a number of nanowires in the chip, the device is then ready for low temperature measurements

Development of a nanogap fabrication method for applications in nanoelectromechanical systems and nanoelectronics

There is a great need for a well-controlled nanogap fabrication technique compatible with NEMS applications. Theoretically, a displacement sensor based on vacuum tunnel junction or a nanogap can be capable of performing quantum-limited measurements in NEMS applications. Additionally, in the context of nanoelectronics, nanogaps are widely demanded to characterize nanostructures and to incorporate them into nanoscale electronic devices. Here, we have proposed and implemented a fabrication technique based on the controlled shrinkage of a lithographically defined gap between two suspended structures by thermal evaporation. We have consistently produced rigid and stable metallic vacuum tunneling junctions at nanometer or subnanometer sizes. The fabricated nanogaps were characterized by I-V measurements and their gap sizes and potential barrier heights were interrogated using the Simmons' model. Throughout this work, high tensile stress silicon nitride thin films were preferred for the fabrication of suspended structures because they have high resonance frequencies with low dissipation, they are mechanically stable, and they are resilient to stiction problem. However, high-stress nitride structures experience a complex shape deformation once they are suspended. The shape deformation is undesired when the precise positioning of the structures is required as in nanogap fabrication. We developed a new method in which the built in stress gradient is utilized to tune the distance between two suspended structures. The technique was simulated by finite element analysis and experimentally implemented to demonstrate a gap tuning capability beyond the lithographic resolution limits

Electron Quantum Tunneling Sensors

Quantum tunneling sensors are typically ultra-sensitive devices which have been specifically designed to convert a stimulus into an electronic signal using the wondrous principles of quantum mechanical tunneling. In the early 1990s, William Kaiser developed one of the first micromachined quantum tunneling sensors as part of his work with the Nasa Jet Propulsion Laboratory. Since then, there have been scattered attempts at utilizing this phenomenon for the development of a variety of physical and chemical sensors. Although these devices demonstrate unique characteristics such as high sensitivity, the principle of quantum tunneling often acts as a double-edged sword and is responsible for certain drawbacks of this sensor family. In this review, we briefly explain the underlying working principles of quantum tunneling and how they are used to design miniaturized quantum tunneling sensors. We then proceed to describe an overview of the various attempts at developing such sensors. Next, we discuss their current need and recent resurgence. Finally, we describe various advantages and shortcomings of these sensors and end this review with an insight into the potential of this technology and prospects.Comment: arXiv admin note: substantial text overlap with arXiv:2006.1279