Electrostatically gated nanofluidic membranes: Technological developments and use of electrochemically polarizable materials

Solid-state nanoporous membranes able to control ionic flows at the molecular level could have important applications in fields of research such as water filtration, nanomedicine, energy production, drug delivery, and bio-chemical analysis. The ability to dynamically control the surface charge and the electrical potential inside nanopores extends the range of applications from passive to active devices, such as nanofluidic transistors. In the first part of the thesis a new wafer-scale manufacturing method for solid-state nanoporous membranes based on casting of sacrificial templates is proposed. This way it is possible to individually define the position and geometry of every nanopore by design, independently from the materials used, whichmake this fabrication strategy adapted to the manufacturing of both passive and active nanofluidic devices. In the second part of the thesis this technology was used to fabricate electrostatically gated nanofluidic membranes with nanopores integrating polarizable electrodes made of amorphous carbon inside the nanochannels. Those membranes demonstrated the ability to modulate the ionic conductivity of the nanopores via the variation of the surface charge of the nanochannels with a sensitivity two-three orders of magnitude larger compared to nanochannels gated through metal-oxide electrodes.

Charge-transport properties of monolayer MoS2 at the interface with dielectric materials

Simone Bertolazzi

Two-dimensional (2D) semiconductors, consisting of single-sheets of layered transition metal dichalcogenides (TMD), are attracting enormous interest from both fundamental science and technology. Monolayer molybdenum disulfide (MoS2), a typical example from this class of materials, is currently under intense research investigation because its direct band gap, atomic-scale thickness and mechanical flexibility could enable a wide range of novel technological applications, such as low-power flexible/transparent electronics, displays and wearable sensors. Critical to all these applications are the material mechanical strength, the mobility of charge-carriers in the 2D semiconductor and its interaction with the surrounding environment. This thesis describes experimental research conducted on these critical aspects and shows a proof-of-concept device application based on heterostructures of MoS2 and graphene. The main goal of the research was to assess experimentally the potential of monolayer MoS2 for application in flexible electronics. The thesis is based on three papers. The first paper describes the measurements of the in-plane stiffness and breaking strength of free-standing membranes of monolayer MoS2. Nanoindentation experiments were performed with the tip of an atomic force microscope (AFM) to extract the material's Young's modulus (E ~ 270 GPa) and breaking strength (Ïmax ~ 23 GPa). Breaking occurred at maximum internal strain Îµint ~ 11%, which indicates that monolayer MoS2 is suitable for integration on flexible plastic substrates. The second paper represents the core work of this thesis. It explores the charge transport properties of monolayer MoS2 supported by different dielectric substrates, such as thin polymer films of parylene, atomically flat sapphire and 2D sheets of hexagonal boron nitride (h-BN). It was found that substrate surface corrugations do not represent a major limit to charge-carrier mobility in monolayer MoS2, which seems at this stage dominated by impurities and material's defects. Field-effect transistors with mobility ~ 100 cm2/Vs and on/off current ratio Ion/Ioff > 10^5 were successfully integrated on parylene substrates, whose root-mean-square roughness Rq can be more than two times larger than the thickness of the transistor channel itself. Because parylene is also a flexible material, this work showed a viable method for the realization of high-mobility and high performance flexible devices based on 2D semiconductors. Finally, the third paper describes a flash-memory cell fabricated using monolayer MoS2/graphene heterostructures and dielectric layers of HfO2 grown by atomic layer deposition (ALD). The architecture of the device resembles that of a floating-gate transistor. Monolayer MoS2 acts as the transistor channel, graphene electrodes are used to collect and inject the charge carriers, and a piece of multilayer graphene serves as ultrathin charge trapping layer. In this paper, it was shown that graphene contacts to monolayer MoS2 result in ohmic-like current-voltage characteristics at room temperature. Moreover, the use of graphene and 2D semiconductors in flash memory technology was indicated as a potential strategy for further scaling of memory cells and for their integration in flexible electronic devices.

EPFL2015

Investigation of Lead-free perovskites for Optoelectronic Application

Alexander Fedorovskiy

The search for new energy sources and materials is at the foundations of scientific and technological progress. These two, often interconnected, fundamental elements open a way to create novel designs and improve existing ones for all types of machines and devices.Perovskite solar cells (PSCs) are a great example of this kind of system. Achievements in halide perovskite materials research made a remarkably rapid growth of energy conversion efficiency in PSC technology possible. In turn, a manufacturing process for the technology is potentially cheaper and more straightforward (relative to Si-based). As a result, the PSCs can be a solid background for producing the next generation of solar cells.However, unfortunately, PSCs are still not ready for a market, primarily because of three problems: large-scale production, stability, and toxicity. The first problem is mainly a result of the rawness of the technology, requires mostly resolving engineering tasks, and is not a fundamental barrier. The second problem â stability has a deeper connection to the properties of the material itself. The nature of degradation processes in PSCs is not completely clear. Still, different studies have found some promising ways to stabilize PSCs for a range of thousands of hours. Thus, a combination of engineering and material research can solve this problem, despite its deeper basis.The third problem, toxicity, is a fundamental property of the high efficient PSCs because of its lead-based compound. Lead is one of the critical components of halide perovskites used in the technology, and at the same time, this metal has confirmed toxicity. The water solubility of lead in halide perovskites (primarily as PbI2 and PbBr2) complicates the situation for the whole lifecycle of the devices - from production to recycling. The toxicity of the materials used in PSCs can affect one of the main goals of solar energy: to be produced safe, clean, and sustainable.Taking into account these facts, I focused this thesis on searching for lead-free alternatives for PSCs.Initially, I focused on searching for a model to predict promising vacancy-ordered double perovskites' formability as part of initial screening. I demonstrated the applicability of the geometrical approach based on Goldschmidt's Tolerance Factor for a simple, easy-to-use formability prediction technique for this class of materials. During this part of the study, I also demonstrated a difference between using the method for classic and vacancy-ordered perovskites.In the next part, I used a novel approach based on deep learning to design a new model of perovskite formability. As a result, I successfully forecast perovskite formability with an accuracy of over 98% for the best case. Moreover, I found that the resulting models were able to find some inaccuracies in the original data.Following, I synthesized and researched the structure and properties of tellurium-based vacancy-ordered perovskites. During the research, I found an unexpected complex situation of the optical gap determination for the materials. To solve this challenge, I demonstrated different approaches of absorption spectra fitting and cross-referenced it with other experimental data.

EPFL2021

Charge-transport properties of monolayer MoS2 at the interface with dielectric materials

Simone Bertolazzi

EPFL2015

Investigation of Lead-free perovskites for Optoelectronic Application

Alexander Fedorovskiy

EPFL2021