Electrochemical Reaction in Single Layer MoS2: nanopores opened atom by atom

Ultrathin nanopore membranes based on 2D materials have demonstrated ultimate resolution toward DNA sequencing. Among them, molybdenum disulfide (MoS2) shows long-term stability as well as superior sensitivity enabling high throughput performance. The traditional method of fabricating nanopores with nanometer precision is based on the use of focused electron beams in transmission electron microscope (TEM). This nanopore fabrication process is time-consuming, expensive, not scalable, and hard to control below 1 nm. Here, we exploited the electrochemical activity of MoS2 and developed a convenient and scalable method to controllably make nanopores in single-layer MoS2 with subnanometer precision using electrochemical reaction (ECR). The electrochemical reaction on the surface of single-layer MoS2 is initiated at the location of defects or single atom vacancy, followed by the successive removals of individual atoms or unit cells from single-layer MoS2 lattice and finally formation of a nanopore. Step-like features in the ionic current through the growing nanopore provide direct feedback on the nanopore size inferred from a widely used conductance vs pore size model. Furthermore, DNA translocations can be detected in situ when as-fabricated MoS2 nanopores are used. The atomic resolution and accessibility of this approach paves the way for mass production of nanopores in 2D membranes for potential solid-state nanopore sequencing.

Probing chemical structures and physical processes with nanopores

Jiandong Feng

This thesis develops and applies the nanopore tool to probe chemical structures and physical processes at the single-molecule level: from single ions to DNA molecules. Nanopore experiments electrically measure the ionic transport through the pore and its modulation from the local environment which can be caused by translocations of an analyte such as objects like DNA molecules or change of the physical conditions such as surface charge. Its precision relies on the physical dimension of the nanopore probe. In this thesis, the atom by atom engineering of single-layer molybdenum disulfide (MoS2) nanopores was achieved using transmission electron microscopy (TEM) or controlled electrochemical reaction (ECR), which further enabled the following investigations. On the translational side, the key driver of the application of nanopores is single molecule DNA sequencing. The sequence of DNA can be extracted based on the modulation of ionic current through the pore by individual nucleotides. To this end, we realized for the first time with solid-state nanopores, identification of all four types of nucleotides by introducing an ionic liquid based viscosity gradient system to control the translocation dynamics. This method provides a potential route for sequencing with solid-state nanopores. On the fundamental side, nanopore experiments could probe physics of single ion transport and with subnanometer pores, we discovered Coulomb blockade for the first time in ionic transport, as the counterpart of quantum dots, and proposed a new mesoscopic understanding for biological ion channel transport. From an engineering perspective, measurement with a single nanopore can avoid averaging over many pores and allow accurately identifying individual parameters for membrane-based processes. With single-layer MoS2 nanopores, we realized the first exploration of a two-dimensional (2D) membrane for osmotic power generation. This thesis demonstrates that nanoscopic, atomically thin pores allow for the exploration of applications in DNA sequencing and investigations of fundamental ion transport for biological ion channels and membrane-based processes.

EPFL2016

Atomically Thin Molybdenum Disulfide Nanopores with High Sensitivity for DNA Translocation

Jiandong Feng, Andras Kis, Ke Liu, Aleksandra Radenovic

Atomically thin nanopore membranes are considered to be a promising approach to achieve single base resolution with the ultimate aim of rapid and cheap DNA sequencing. Molybdenum disulfide (MoS2) is newly emerging as a material complementary to graphene due to its semiconductive nature and other interesting physical properties that can enable a wide range of potential sensing and nanoelectronics applications. Here, we demonstrate that monolayer or few-layer thick exfoliated MoS2 with subnanometer thickness can be transferred and suspended on a predesigned location on the 20 nm thick SiNx. membranes. Nanopores in MoS2 are further sculpted with variable sizes using a transmission electron microscope (TEM) to drill through suspended portions of the MoS2 membrane. Various types of double-stranded (ds) DNA with different lengths and conformations are translocated through such a novel architecture, showing improved sensitivity (signal-to-noise ratio >10) compared to the conventional silicon nitride (SiNx) nanopores with tens of nanometers thickness. Unlike graphene nanopores, no special surface treatment is needed to avoid hydrophobic interaction between DNA and the surface. Our results imply that MoS2 membranes with nanopore can complement graphene nanopore membranes and offer potentially better performance in transverse detection.

Amer Chemical Soc2014

Electrochemical and morphological engineering of 2D materials for nanopore sensing

Martina Lihter

Nanopores are nanometer-sized holes that were initially proposed for DNA sequencing. Several years ago sequencing was made possible with biological nanopores. However, solid-state nanopores have plenty of advantages to offer compared to their biological counterparts. This thesis focuses on nanopores made in 2D materials, and their sensing capabilities. They provide an outstanding spatial resolution and a good signal-to-noise ratio (SNR) for sensing. As a 2D semiconductor, molybdenum disulfide (MoS2) exhibits unique (opto)electronic and electrochemical properties. The electronic band structure of a semiconducting MoS2 results in highly sensitivity to its chemical environment and external electric field. Therefore, monitoring the transverse current through the MoS2 during analyte translocation can provide a powerful sensing mechanism. As an n-type semiconductor, MoS2 exhibits a characteristic electrochemical behavior: it shows electrochemical activity when polarized cathodically, while in the anodic region becomes electrochemically inactive. This thesis covers five topics in which I demonstrate how the properties of 2D materials can be used for designing advanced sensing platforms for biosensing. Fabrication of MoS2 Nanopores. Here, we give an overview of a reliable fabrication process optimized for the production of high-quality devices. We discuss the main issues, how to solve and avoid them. In the end, we demonstrate applications of MoS2 nanopores for sensing and for osmotic power generation. Geometrical Effect in 2D Nanopores. We compare two different pore geometries: triangular pores in hexagonal boron-nitride (h-BN) vs. approximately circular pores in MoS2. In h-BN nanopores, we observe a lower conductance drop caused by DNA translocation, than expected from a conventional conductance model. As an explanation, we propose a reduced ion-concentration and ion-mobility inside the pore, supported by molecular dynamics simulations. Transverse Detection of DNA in MoS2 Nanopore. This chapter presents the realization of a hybrid nanopore-FET device, consisting of an MoS2 ribbon and a nanopore drilled in it. Such a device acts as a field-effect transistor (FET), where the transverse current through the MoS2 is modulated by the translocating molecule and the ionic voltage applied across the pore. We show that the transverse current is more sensitive to DNA translocation than the ionic current. Passivation of Electrodes Contacting MoS2. The method is based on the electrochemical deposition of a polymer, which blocks the electron transfer from the surface of the electrodes to ions in solution. To avoid the deposition on MoS2, we used poly(phenylene oxide) (PPO) that polymerizes in the potential window where MoS2 is inactive. Deposition is compatible with MoS2 and highly area-selective, even at the nanoscale, as we demonstrate on the nanoelectrodes of a nanopore-FET device. Electrochemical Modification of MoS2. By polarizing MoS2 cathodically, it is possible to electrochemically deposit a thin layer of aryl-diazonium compounds on MoS2 surface. This approach allows to introduce specific chemical groups on MoS2 and nanopore rim, which could be used for specific recognition of analytes as they translocate through the pore. Furthermore, since the deposition occurs only on the MoS2 to which the voltage was applied, this could enable specific functionalization of adjacent nanoribbons in nanopore-FET devices.