The charge and energy transfer properties are essential in semiconductors[
Chinese Journal of Lasers, Volume. 50, Issue 1, 0113009(2023)
[in Chinese]
In recent years, two-dimensional (2D) materials have attracted extensive interests due to the large exciton binding energy different from bulk materials. Many peculiar properties have been discovered that have far-reaching perspectives in the next generation of optoelectronic devices. In this review, we introduce the forms of exciton existence in 2D materials and several promising 2D materials with good applications at first. Then, we summarize relevant contemporary tools for probing exciton dynamics and methods of regulating 2D exciton transport, for instance, electrical regulation, stress/surface wave regulation and moiré potential regulation, etc. Finally, we conclude the general development of regulation in 2D materials and propose several possible opportunities of application prospect.In recent years, two-dimensional (2D) materials have attracted extensive interests due to the large exciton binding energy different from bulk materials. Many peculiar properties have been discovered that have far-reaching perspectives in the next generation of optoelectronic devices. In this review, we introduce the forms of exciton existence in 2D materials and several promising 2D materials with good applications at first. Then, we summarize relevant contemporary tools for probing exciton dynamics and methods of regulating 2D exciton transport, for instance, electrical regulation, stress/surface wave regulation and moiré potential regulation, etc. Finally, we conclude the general development of regulation in 2D materials and propose several possible opportunities of application prospect.
1 Introduction
The charge and energy transfer properties are essential in semiconductors[
Since the first mechanical exfoliation of graphene from graphite by Geim in 2004[
The exciton binding energy of 2D semiconductor materials is usually particularly large due to the weakening of Coulomb shielding effect[
Therefore,the study of exciton dynamics in 2D materials is of great significance. However,a systematic overview of the relevant regulating methods has rarely been reported. In this review,we focus on several emerging classes of 2D materials and their heterostructures. Firstly,we introduce the intrinsic principles of exciton diffusion in 2D materials and the tools to probe exciton diffusion. Then,we review the electrical regulation,stress/surface wave regulation,moiré potential regulation and some other potential regulating methods of exciton diffusion in recent years. Finally,we summarize the recent research,and provide some discussion of the challenges and prospects in the future.
2 Intrinsic Principle of Exciton Diffusion
There are two typical cases of exciton states in semiconductors:one is the Frenkel exciton,where the electron-hole pair binding energy is large and the exciton Bohr radius is small and localized to the molecule[
In semiconductors,we usually use Einstein relation to describe exciton diffusion[
where
To further understand the exciton diffusion in 2D materials with carrier lattice interactions,a large number of theoretical and experimental researches have been carried out[
Due to the short lifetime of excitons and the aforementioned effects of phonon scattering and defect compounding,it is not easy to test the exciton transport experimentally. In this article,the favorable tools for probing the exciton transport properties mainly include time-resolved photoluminescence(TRPL)spectroscopy[
Population distribution corresponds to the diffusion length. The specific principle is traced back to the intrinsic diffusion equation,with the probability density distribution satisfying
where
where
In most cases,the initial distribution can be fitted by a Gaussian distribution. Through the initial distribution,the peak density
in which the spatial variance
Finally,the mean square displacement(MSD)DMS grows linearly with time:
The MSD equation indicates the relationship between population distribution and diffusivity. Most researchers study carrier diffusion phenomena by characterizing the diffusivity in this way[
It can be concluded that by the above tools,we can obtain the diffusivity of carriers in any materials. However,the carrier transport process is not always smooth. In general,the carrier transport process is affected by electron-phonon coupling and defect scattering[
3 Methods of Regulating Exciton Diffusion
Regulation of exciton diffusion has attracted much attention in recent years. The ability to freely control the exciton transport behavior is useful for understanding exciton dynamics processes in 2D materials and for applications in optoelectronic devices. We mainly consider the transport dynamics regulated by exciton itself and surrounding environment. Regulation by exciton itself mainly uses bias electric field to change the kinetic energy(acceleration)or self-energy(trion)of the exciton. Regulation by surrounding environment mainly uses strain to influence the potential field around the exciton or to build a new potential field(moiré potential). So,we have chosen to discuss these types of regulation. In terms of applications,the most common method of regulation is to apply electric field. For optoelectronic devices,external stress is also a major factor affecting the performance and lifetime of the device. Understanding the effect of applied stress on exciton diffusion can provide assistance to improve device stability. At the same time,applying it to modulate diffusion can further optimize the design of future devices. In addition,the moiré potential is the properties of the material itself,and the regulation method using its own properties is beneficial for applying the material to any scenario. Finally,we summarize some other modulation means,all of which have some influence on the diffusion and are worth taking into account when regulating the exciton diffusion.
3.1 Electrical Regulation
Because of the simple response of carriers to electric fields,regulation of carrier transport by electric fields is the most common method. In 2008,High et al.[
To understand the transport dynamics of neutral exciton and trion,Kato et al.[
Figure 1.Transition and electrical control of neutral exciton and trions in 2D materials. (a) PL spectrum of monolayer WS2 at 4.5-275 K, where the blue and red parts are fitted to the neutral exciton and trion components, respectively[57]; (b)-(d) MoS2 PL intensity distribution variance as function of time at different back-gate voltage (Vg=-20, 0, 20 V)[60]; (e) trion formation and schematic diagram of the monolayer WS2[61]; (f) drift distances of the trions as function of the dacay time at different applied bias (Vext=20, 40, 60 V)[61]; (g) the peak position of the PL emission as function of decay time at applied bias Vext=-60 V and 60 V[61]
Based on the understanding of the transition between trions and neutral excitons,Uddin et al.[
where
The properties of a single material are always limited. Currently,the more popular material is van der Waals heterostructure,about which we will describe in detail later. There are also many applications of electric field modulation on such structures,but most of them are for the study of interlayer exciton transport,with few reports on trion correlation[
3.2 Stress/Surface Wave Regulation
During the preparation and application of electronic devices,strain forces are inevitably generated on the material. How to recognize the effect of stress on exciton transport in 2D materials and to apply it skillfully becomes a topic worthy of consideration. Currently,the effect of strain on 2D materials is mainly studied by applying pressure to both sides of the 2D material to produce tensile strain[
TMDC,by virtue of its high sensitivity to external strain,is well suited for room temperature directed transit of direct excitons under dynamic strain only. Datta et al.[
Figure 2.Control of exciton flux by SAWs at room temperature. (a),(b) Real-space PL mapping of bilayer WSe2 when SAW is off (a) and when SAW is on with 6 mW power (b); (c) schematic illustration of hBN encapsulated bilayer WSe2 stacked on SAW devices[73]. (d) Schematic of strain induced diffusion of excitons in monolayer WS2; (e) large diffusion length due to exciton-exciton annihilation by one exciton providing additional kinetic energy to another; (f) diffusion length of neutral excitons as function of generation rates in monolayer WS2 at different strains (ε=0, 0.5%)[75]
In addition to the modulation of exciton transport by SAWs,the use of stress-generated strain can also manipulate exciton transport behavior. Due to the lattice-distortions and the multi-valley excitonic landscape,the variation of diffusion with strain is not linear,where multibody interactions should be considered[
3.3 Moiré Potential Regulation
The van der Waals heterojunction stacked by TMDCs is the current mainstream heterostructure[
In TMDCs heterostructures,the applied periodic potential field introduced by the material lattice mismatch or the relative interlayer twisting is called exciton moiré potential. It can regulate the physical properties of the interlayer excitons in the TMDCs system[
Figure 3.Interlayer exciton transport modulated by moiré potentials. (a),(b) Schematic plot of the moiré potential in MoSe2/WSe2 heterostructures, with twist angles near 0° (H-type) and 60° (R-type); (c) interlayer exciton diffusivity as function of temperature with twist angles of 0.15° (purple), 2.49° (green), 5.12° (yellow), and 53.9° (blue)[89]. (d) Illustration of different stackings from hBN/graphene moiré superlattice; (e) MSD of exciton density distribution in bare WSe2 on SiO2/Si substrate (blue dots), PDMS-WSe2 on SiO2/Si substrate (black diamonds) and hBN encapsulated WSe2 (red squares), where inset plots diffusivities as function of time for three samples; (f) comparison of exciton diffusivities with and without graphene layer[91]
where
In addition to changing the twist angle,adjusting the distance between layers and the dielectric surroundings can also cause a variance in moiré potential[
Because the modulation of angle or surrounding is not easy,the effect of altering the moiré potential by twist angle or interlayer distance on exciton transport is limited. On the basis of modulating the moiré potential,manipulating the localization-delocalization transition of the interlayer excitons by using an applied electric field,active modulation of their spatial diffusion behavior is expected[
3.4 Other Regulations
Apart from the above-mentioned widely studied modulators,there are actually some other methods of regulating exciton dynamics.
Varying the excitation power and the temperature is a universal method. It has been reported that,at low excitation power,excitons show subdiffusion because of the presence of defect states,while at high excitation power,the exciton density increases and the defective states are filled,so that they show normal diffusion,which is totally different from TMDCs[
Changing the number of layers is also a recently common method,especially in heterostructures. Conventional TMDCs out-of-plane heterojunctions use two different layers of materials. Producing more intralayer excitons by increasing the thickness of one layer can enhance the correlation between the intralayer and interlayer excitons,which will lead to more interesting transport processes[
2D material is a good platform for valley exciton dynamics. Because the monolayer structure of 2D materials breaks the spatial inversion symmetry and the material has strong spin-orbit coupling,a unique spin-valley locking effect is formed. However,the spin-valley exciton dynamics in 2D materials is very complex. Different physical mechanisms such as many-body effects of electron-hole interactions,electro-phonon coupling and spin-orbit coupling are involved[
In addition to the diffusion properties of excitons,the exciton-polariton systems formed by the coupling of excitons and photons also exhibit fantastic dynamic properties. However,characterizing exciton-polariton is not an easy task. It is generally necessary to directly characterize the exciton-polariton system by forming microcavity exciton-polariton through microcavity coupling. Recently,Ferreira et al.[
4 Conclusions
In summary,we present the modulation of carrier transport in several currently dominant 2D materials and the corresponding heterojunctions. Excitons in 2D materials can be modulated by a variety of means to enhance performance. The electrical regulation allows understanding the transition relationship between trions and neutral excitons. Recently the modulation of the transition between trions and neutral excitons can be achieved by orbital angular momentum light,which will be beneficial to the design of future electronic devices to some extent. SAWs modulation of exciton transport properties can effectively drive the periodic diffusion behavior of excitons,and the realization of traversing the entire material is expected. In addition,the generation of lattice strain by means of external stress is a current topic worthy of further excavation. Heterojunction is the mainstream structure of 2D materials as electronic devices nowadays,and the moiré potential caused by lattice mismatch inevitably becomes the main means to regulate the carrier dynamics in electronic devices. The moiré potential shift brought by the twist angle effectively promotes the diffusion of interlayer excitons,which provides ideas to design excellent device structures in the future. In addition,some potential regulation methods deserve more consideration,such as varying the optical power,the number of material layers,modulating valley exciton diffusion,exciton-polariton diffusion,etc. Recently,in-plane heterojunctions have become a topic worth exploring,as the carrier mobility is likely to reach ten times that of out-of-plane heterojunctions due to the weak binding of excitons by edge states. These can propose possible development in the direction of future electronic devices and solar cells,etc. In fact,the modulation of exciton diffusion behavior by means of applied fields still has limitations. Then,the modulation of exciton behavior by changing the structure of the material itself may become a major challenge for future exciton diffusion modulation,and the long-range directional transport of excitons is expected to be realized by processing the structure and changing the kinetic process of excitons,which has a fantastic prospect for future optoelectronic devices.
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Yuexing Xia, Shuai Zhang, Keming Wu, Yiyang Gong, Shuai Yue, Xinfeng Liu. [J]. Chinese Journal of Lasers, 2023, 50(1): 0113009
Category: micro and nano optics
Received: Sep. 18, 2022
Accepted: Oct. 27, 2022
Published Online: Jan. 13, 2023
The Author Email: Yue Shuai (yueshuai@nanoctr.cn), Liu Xinfeng (liuxf@nanoctr.cn)