<div>Recently, atomically thin two-dimensional (2D) layered materials such as graphene and transition metal dichalcogenides (TMDCs) have emerged as a new class of materials due to their unique electronic structures and optical properties at the nanoscale limit. 2D materials also hold great promises as building blocks for creating new heterostructures for optoelectronic applications such as atomically thin photovoltaics, light emitting diodes, and photodetectors. Understanding the fundamental photo-physics process in 2D semiconductors and heterostructures is critical for above-mentioned applications. </div><div>In Chapter 1, we briefly describe photo-generated charge carriers in two-dimensional (2D) transition metal dichalcogenides (TMDCs) semiconductors and heterostructures. Due to the reduced dielectric screening in the single-layer or few-layer of TMDCs semiconductors, Columbo interaction between electron and hole in the exciton is greatly enhanced that leads to extraordinary large exciton binding energy compared with bulk semiconductors. The environmental robust 2D excitons provide an ideal platform to study exciton properties in TMDCs semiconductors. Since layers in 2D materials are holding by weak van de Waals interaction, different 2D layers could be assembled together to make 2D heterostructures. The successful preparation of 2D heterostructures paves a new path to explore intriguing optoelectronic properties.</div><div>In Chapter 2, we introduce various optical microscopy techniques used in our work for the optical characterization of 2D semiconductors and heterostructures. These optical imaging tools with high spatial and temporal resolution allow us to directly track charge and energy flow at 2D interfaces.</div><div>Exciton recombination is a critical factor in determining the efficiency for optoelectronic applications such as semiconductor lasers and light-emitting diodes. Although exciton dynamics have been investigated in different 2D semiconductor, large variations in sample qualities due to different preparation methods have prevented obtaining intrinsic exciton lifetimes from being conclusively established. In Chapter 3, we study exciton dynamics in 2D TMDCs semiconductors using ultrafast PL and transient absorption microscopy. Here we employ 2D WS2 semiconductor as a model system to study exciton dynamics due to the low defect density and high quantum yield of WS2. We mainly focus on how the exciton population affects exciton dynamics. At low exciton density regime, we demonstrate how the interlayer between the bright and dark exciton populations influence exciton recombination. At high exciton density regime, we exhibit significant exciton-exciton annihilation in monolayer WS2. When comparing with the bilayer and trilayer WS2, the exciton-exciton annihilation rate in monolayer WS2 increases by two orders of magnitude due to enhanced many-body interactions at single layer limit. </div><div>Long-range transport of 2D excitons is desirable for optoelectronic applications based on TMDCs semiconductors. However, there still lacks a comprehensive understanding of the intrinsic limit for exciton transport in the TMDCs materials currently. In Chapter 4, we employ ultrafast transient absorption microscopy that is capable of imaging excitons transport with ~ 200 fs temporal resolution and ~ 50 nm spatial precision to track exciton motion in 2D WS2 with different thickness. Our results demonstrate that exciton mobility in single layer WS2 is largely limited by extrinsic factors such as charge impurities and surface phonons of the substrate. The intrinsic phonon-limited exciton transport is achieved in WS2 layers with a thickness greater than 20 layers.</div><div>Efficient photocarrier generation and separation at 2D interfaces remain a central challenge for many optoelectronic applications based on 2D heterostructures. The structural tunability of 2D nanostructures along with atomically thin and sharp 2D interfaces provides new opportunities for controlling charge transfer (CT) interactions at 2D interfaces. A largely unexplored question is how interlayer CT interactions contribute to interfacial photo-carrier generation and separation in 2D heterostructures. In Chapter 5, we present a joint experimental and theoretical study to address carrier generation from interlayer CT transitions in WS2-graphene heterostructures. We use spatially resolved ultrafast transient absorption microscopy to elucidate the role of interlayer coupling on charge transfer and photo-carrier generation in WS2-graphene heterostructures. These results demonstrate efficient broadband photo-carrier generation in WS2-graphene heterostructures which is highly desirable for atomically thin photovoltaic and photodetector applications based on graphene and 2D semiconductors.</div><div>CT exciton transport at heterointerfaces plays a critical role in light to electricity conversion using 2D heterostructures. One of the challenges is that direct measurements of CT exciton transport require quantitative information in both spatial and temporal domains. In order to address this challenge, we employ transient absorption microscopy (TAM) with high temporal and spatial resolution to image both bright and dark CT excitons in WS2-tetrance and CVD WS2-WSe2 heterostructure. In Chapter 6, we study the formation and transport of interlayer CT excitons in 2D WS2-Tetracene vdW heterostructures. TAM measurements of CT exciton transport at these 2D interfaces reveal coexistence of delocalized and localized CT excitons. The highly mobile delocalized CT excitons could be the key factor to overcome large CT exciton binding energy in achieving efficient charge separation. In Chapter 7, we study stacking orientational dependent interlayer exciton recombination and transport in CVD WS2-WSe2 heterostructures. Temperature-dependent interlayer exciton dynamics measurements suggest the existence of moiré potential that localizes interlayer excitons. TAM measurements of interlayer excitons transport reveal that CT excitons at WS2-WSe2 heterointerface are much more mobile than intralayer excitons of WS2. We attributed this to the dipole-dipole repulsion from bipolar interlayer excitons that efficiently screen the moiré potential fluctuations and facilitate interlayer exciton transport. Our results provide fundamental insights in understanding the influence of moiré potential on interlayer exciton dynamics and transport in CVD WS2-WSe2 heterostructures which has important implications in optoelectronic applications such as atomically thin photovoltaics and light harvesting devices. </div><div><br></div>

<p dir="ltr">In the realm of two-dimensional (2D) materials, monolayer (ML) transition metal dichalcogenides (TMDCs) have gained significant interest due to their direct bandgap transition, high carrier mobility, strong light-matter interaction, and robust spin and valley degrees of freedom, starkly contrasting their bulk counterparts. Owing to their large surface-to-volume ratio, the integration of ML TMDCs with other various 2D semiconductors and microcavities offers opportunities to study fundamental photo-physics processes at the heterointerfaces, paving the way for implementation of next-generation devices.</p><p dir="ltr">Chapter 1 provides a concise introduction to 2D materials, particularly TMDCs, and their fascinating optical and electronic properties. It examines the role of excitons in 2D materials, and the impact of energy transfer (ET) and charge transfer (CT) on exciton’s properties in TMDC through the construction of 2D van der Waals (vdW) heterostructures and coupling with optical microcavities. This chapter also delves into the potential enhancement of TMDCs’ optical properties by integrating 2D hybrid lead halide perovskites and ultra-thin three-dimensional (3D) halide perovskites with TMDCs. Furthermore, it sets the general context for light-matter interaction, another form of ET, considering both weak and strong coupling regimes.</p><p dir="ltr">Chapter 2 outlines the optical techniques employed to gather data for this work. A focus is placed on ultrafast optical techniques like transient absorption spectroscopy, which allow for direct probing and analysis of ET and CT dynamics at the heterointerface.</p><p dir="ltr">Photoinduced interfacial CT plays a critical role in the field of energy conversion involving vdW heterostructures constructed by inorganic nanostructures and organic materials. However, the control of atomic-scale stacking configurations to modulate charge separation at interfaces remains challenging. Chapter 3 aims to illustrate tunability of interfacial charge separation in a Type-II heterojunction between ML-WS₂ and an organic semiconducting molecule by rational design of relative stacking configurations using 2D perovskites as scaffoldings. This chapter investigates how different molecular stacking, face-to-face versus face-to-edge, affects CT at the heterointerface. Our findings reveal that the CT process heavily depends on the relative stacking configurations at the organic-TMDCs heterointerface, with charge separation being notably slowed down for face-to-edge configuration compared to face-to-face configuration. These investigations open new opportunities for designing efficient charge separation processes in energy conversion applications by judiciously engineering interfaces between organic and inorganic semiconductors, using 2D perovskites as scaffolds.</p><p dir="ltr">Though TMDCs’ large surface-to-volume ratios make them excellent platforms for studying interfacial properties, the presence of bulky ligands on the surface of 2D perovskite poses a challenge, impeding direct interfacial coupling in their heterostructures. Chapter 4 details the fabrication of ML-WS₂ and ultra-thin CH₃NH₃PbX₃ (MAPbX₃, X=Br, I) heterostructures with tunable energy levels, to study the dynamics of CT and ET at these hybrid interfaces. Notably, heterojunctions of WS₂ with pure MAPbBr₃ and MAPbI₃ were elucidated as Type-I and Type-II respectively, using photoluminescence (PL) and time-resolved photoluminescence (TR-PL) measurements. Transit absorption (TA) spectroscopy investigations unambiguously revealed a rapid ET facilitated by CT in the WS₂/MAPbBr₃ heterostructure, with a time constant of ~20 ps, and a predominantly CT in the WS₂/MAPbI₃ heterostructure with a time constant of ~50 femtosecond (fs). The successful interfacing of low-dimensional perovskites with an extensive array of traditional 2D materials such as TMDCs opens up possibilities for novel optoelectronic properties and applications within the field of 2D material systems. Furthermore, the ultrafast and efficient ET and CT processes hold promise for the creation of advanced energy conversion devices.</p><p dir="ltr">In the last chapter, we successfully fabricated a ML-WS₂ in conjunction with a silver (Ag) nanoparticle (NP) array. Our findings affirmed a weak light-matter coupling between ML-WS₂ and the Ag NP array, as evidenced by angle-resolved photoluminescence spectroscopy. Furthermore, an enhancement in the bright exciton emission from ML-WS₂ was observed at reduced temperatures. The analysis of PL enhancement factor at varying temperatures suggested that an upper bound of the enhancement factor for the bright exciton could reach ~51 or even higher at 7 K, given the imperfect uniformity of the electric filed generated around the NPs. This discovery carries significant implications for the manipulation of excitons in TMDCs and expands their potential applications in the field of optoelectronics.</p>