Low-dimensional Material: Structure-property Relationship and Applications in Energy and Environmental Engineering

In the past several decades, low-dimensional materials (0D materials, 1D materials and 2D materials) have attracted much interest from both the experimental and theoretical points of view. Because of the quantum confinement effect, low-dimensional materials have exhibited a kaleidoscope of fascinating phenomena and unusual physical and chemical properties, shedding light on many novel applications. Despite the enormous success has been achieved in the research of low-dimensional materials, there are three fundamental challenges of research in low-dimensional materials: 1) Develop new computational tools to accurately describe the properties of low-dimensional materials with low computational cost. 2) Predict and synthesize new low-dimensional materials with novel properties. 3) Reveal new phenomenon induced by the interaction between low-dimensional materials and the surrounding environment. In this thesis, atomistic modelling tools have been applied to address these challenges. We first developed ReaxFF parameters for phosphorus and hydrogen to give an accurate description of the chemical and mechanical properties of pristine and defected black phosphorene. ReaxFF for P/H is transferable to a wide range of phosphorus and hydrogen containing systems including bulk black phosphorus, blue phosphorene, edge-hydrogenated phosphorene, phosphorus clusters and phosphorus hydride molecules. The potential parameters were obtained by conducting global optimization with respect to a set of reference data generated by extensive ab initio calculations. We extended ReaxFF by adding a 60° correction term which significantly improved the description of phosphorus clusters. Emphasis was placed on the mechanical response of black phosphorene with different types of defects. Compared to the nonreactive SW potential of phosphorene, ReaxFF for P/H systems provides a significant improvement in describing the mechanical properties of the pristine and defected black phosphorene, as well as the thermal stability of phosphorene nanotubes. A counterintuitive phenomenon was observed that single vacancies weaken the black phosphorene more than double vacancies with higher formation energy. Our results also showed that the mechanical response of black phosphorene is more sensitive to defects in the zigzag direction than that in the armchair direction. Since ReaxFF allows straightforward extensions to the heterogeneous systems, such as oxides, nitrides, the proposed ReaxFF parameters for P/H systems also underpinned the reactive force field description of heterogeneous P systems, including P-containing 2D van der Waals heterostructures, oxides, etc. Based on the evolutionary algorithm driven structural search, we proposed a new stable trisulfur dinitride (S3N2) 2D crystal that is a covalent network composed solely of S-N σ bonds. S3N2 crystal is dynamically, thermally and chemically stable as confirmed by the computed phonon spectrum and ab initio molecular dynamics simulations. GW calculations showed that the 2D S3N2 crystal is a wide, direct band-gap (3.92 eV) semiconductor with a small hole effective mass. The anisotropic optical response of 2D S3N2 crystal was revealed by GW-BSE calculations. Our result not only marked the prediction of the first 2D crystal composed of nitrogen and sulfur, but also underpinned potential innovations in 2D electronics, optoelectronics, etc. Inspired by the discovery of S3N2 2D crystal, we proposed a new 2D crystal, diphosphorus trisulfide (P2S3), based on the extensive evolutionary algorithm driven structural search. The 2D P2S3 crystal was confirmed to be dynamically, thermally and chemically stable by the computed phonon spectrum and ab initio molecular dynamics simulations. This 2D crystalline phase of P2S3 corresponds to the global minimum in the Born-Oppenheimer surface of the phosphorus sulfide monolayers with 2:3 stoichiometry. It is a wide band gap (4.55 eV) semiconductor with P-S σ bonds. The electronic properties of P2S3 structure can be tuned by stacking into multilayer P2S3 structures, forming P2S3 nanoribbons or rolling into P2S3 nanotubes, expanding its potential applications for the emerging field of 2D electronics. Then we showed that the hydrolysis reaction is strongly affected by relative humidity. The hydrolysis of CO32- with n = 1-8 water molecules was investigated by ab initio method. For n = 1-5 water molecules, all the reactants follow a stepwise pathway to the transition state. For n = 6-8 water molecules, all the reactants undergo a direct proton transfer to the transition state with overall lower activation free energy. The activation free energy of the reaction is dramatically reduced from 10.4 to 2.4 kcal/mol as the number of water molecules increases from 1 to 6. Meanwhile, the degree of the hydrolysis of CO32- is significantly increased compared to the bulk water solution scenario. The incomplete hydration shells facilitate the hydrolysis of CO32- with few water molecules to be not only thermodynamically favorable but also kinetically favorable. We showed that the chemical kinetics is not likely to constrain the speed of CO2 air capture driven by the humidity-swing. Instead, the pore-diffusion of ions is expected to be the time-limiting step in the humidity driven CO2 air capture. The effect of humidity on the speed of CO2 air capture was studied by conducting CO2 absorption experiment using IER with a high ratio of CO32- to H2O molecules. Our result is able to provide valuable insights to designing efficient CO2 air-capture sorbents. Lastly, the self-assembly mechanism of one-end-open carbon nanotubes (CNTs) suspended in an aqueous solution was studied by molecular dynamics simulations. It was shown that two one-end-open CNTs with different diameters can coaxially self-assemble into a nanocapsule. The nanocapsules formed were stable in aqueous solution under ambient conditions, and the pressure inside the nanocapsule was much higher than the ambient pressure due to the van der Waals interactions between two parts of the nanocapsule. The effects of the normalized radius difference, normalized inter-tube distance and aspect ratio of the CNT pairs were systematically explored. The electric field response of nanocapsules was studied with ab initio molecular dynamics simulations, which showed that nanocapsules can be opened by applying an external electric field, due to the polarization of carbon atoms. This discovery not only shed light on a simple yet robust nanocapsule self-assembly mechanism, but also underpinned potential innovations in drug delivery, nano-reactors, etc

Film formation mechanism uncovered in 2D/3D mixed-dimensional lead halide perovskites

2D layered metal halides can be added to 3D perovskites to improve the long-term stability of hybrid perovskite solar cells. The presence of the low-dimensional material alters the film formation mechanism. In this issue of Chem, Kanatzidis and collaborators investigate in situ the crystallization mechanism of mixed-dimensional 2D/3D lead-based perovskite films

Quantum Transport and Band Structure Evolution under High Magnetic Field in Few-Layer Tellurene

Quantum Hall effect (QHE) is a macroscopic manifestation of quantized states which only occurs in confined two-dimensional electron gas (2DEG) systems. Experimentally, QHE is hosted in high mobility 2DEG with large external magnetic field at low temperature. Two-dimensional van der Waals materials, such as graphene and black phosphorus, are considered interesting material systems to study quantum transport, because it could unveil unique host material properties due to its easy accessibility of monolayer or few-layer thin films at 2D quantum limit. Here for the first time, we report direct observation of QHE in a novel low-dimensional material system: tellurene.High-quality 2D tellurene thin films were acquired from recently reported hydrothermal method with high hole mobility of nearly 3,000 cm2/Vs at low temperatures, which allows the observation of well-developed Shubnikov-de-Haas (SdH) oscillations and QHE. A four-fold degeneracy of Landau levels in SdH oscillations and QHE was revealed. Quantum oscillations were investigated under different gate biases, tilted magnetic fields and various temperatures, and the results manifest the inherent information of the electronic structure of Te. Anomalies in both temperature-dependent oscillation amplitudes and transport characteristics were observed which are ascribed to the interplay between Zeeman effect and spin-orbit coupling as depicted by the density functional theory (DFT) calculations

Low-Dimensional Material Devices For Atomic Defect Engineering, Ionic And Molecular Transport

With the advancement of nanofabrication techniques and the growth and synthesis of novel low-dimensional materials, such graphene and transition metal dichalcogenides, it is possible to probe the fundamental principles of ion and molecule transport down to the single-atom scale. Understanding these ionic and atomic interactions during molecular transport at an atomic level play a pivotal role in developing solid-state aquaporins or bio- mimicking artificial membrane proteins channels. Apart from biological processes in living cells, ionic transport plays a vital role in membrane-based technologies such as water purification, desalination, separation techniques and energy harvesting. This thesis focuses on developing low-dimensional devices and creating sub-nanometer pores or point defects for exploring molecular and ionic transport phenomena at an atomic scale. Additionally, defect engineering of such point defects also has potential quantum applications, including quantum sensing and computation. First, I discuss the fabrication process of these low-dimensional devices, including 2D materials growth, transfer with the help of nanofabrication techniques and various characterization modes. Further, in this regime of angstrom-scale confinements, I investigate ionic transport phenomenon in monolayer 2D materials with single sub-nanometer pore and an ensemble of sub-nanometer pores and report experimental results showing strong deviation from continuum physics. Macroscopic quantities such as bulk ion concentration for these angstrom-size systems become insufficient to explain features of the measured ion conductance and its scaling with experimental parameters such as ion concentration and surface charge of the pore (edge atoms)

Emergence of Room-Temperature Ferroelectricity at Reduced Dimensions

The enhancement of the functional properties of materials at reduced dimensions is crucial for continuous advancements in nanoelectronic applications. Here, we report that the scale reduction leads to the emergence of an important functional property – ferroelectricity, challenging the long-standing notion that ferroelectricity is inevitably suppressed at the scale of a few nanometers. A combination of theoretical calculations, electrical measurements, and structural analyses provides evidence of room-temperature ferroelectricity in strain-free epitaxial nanometer-thick films of otherwise non-ferroelectric SrTiO3. We show that electrically-induced alignment of naturally existing polar nanoregions is responsible for the appearance of a stable net ferroelectric polarization in these films. This finding can be useful for the development of low-dimensional material systems with enhanced functional properties relevant to emerging nanoelectronic devices

Temperature evolution of domains and intradomain chirality in 1T- TaS2

We use scanning tunneling microscopy to study the temperature evolution of the atomic-scale properties of the nearly commensurate charge density wave (NC-CDW) state of the low-dimensional material 1T-TaS2. Our measurements at 203, 300, and 354 K, roughly spanning the temperature range of the NC-CDW state, show that while the average CDW periodicity is temperature independent, domaining and the local evolution of the CDW lattice within a domain are temperature dependent. Further, we characterize the temperature evolution of the displacement field associated with the recently discovered intradomain chirality of the NC-CDW state by calculating the local rotation vector. Intradomain chirality throughout the NC-CDW phase is likely driven by a strong coupling of the CDW lattice to the atomic lattice. © 2023 American Physical Society

First-principles modelling of materials: from polythiophene to phosphorene

As a result of the computing power provided by the current technology, computational methods now play an important role in modeling and designing materials at the nanoscale. The focus of this dissertation is two-fold: first, new computational methods to model nanoscale transport are introduced, then state-of-the-art tools based on density functional theory are employed to explore the properties of phosphorene, a novel low dimensional material with great potential for applications in nanotechnology. A Wannier function description of the electron density is combined with a generalized Slater-Koster interpolation technique, enabling the introduction of a new computational method for constructing first-principles model Hamiltonians for electron and hole transport that maintain the density functional theory accuracy at a fraction of the computational cost. As a proof of concept, this new approach is applied to model polythiophene, a polymer ubiquitous in organic photovoltaic devices. A new low dimensional material, phosphorene - a single layer of black phosphorous - the phosphorous analogue of graphene was first isolated in early 2014 and has attracted considerable attention. It is a semiconductor with a sizable band gap, which makes it a perfect candidate for ultrathin transistors. Multi-layer phosphorene transistors have already achieved the highest hole mobility of any two-dimensional material apart from graphene. Phosphorene is prone to oxidation, which can lead to degradation of electrical properties, and eventually structural breakdown. The calculations reported here are some of the first to explore this oxidation and reveal that different types of oxygen defects are readily introduced in the phosphorene lattice, creating electron traps in some situations. These traps are responsible for the non-ambipolar behavior observed by experimental collaborators in air-exposed few-layer black phosphorus devices. Calculation results predict that air exposure of phosphorene creates a new family of two-dimensional oxides, which has been later confirmed by X-ray photoemission measurements. These oxides can form protective coatings for phosphorene and have interesting tunable electronic properties. Finally, Wannier function interpolation has been used to demonstrate that a saddle-point van Hove singularity is present near the phosphorene Fermi energy, as observed in some layered cuprate high temperature superconductors; this leads to an intriguing strain-induced ferromagnetic instability