Spin-valley optoelectronics based on two-dimensional materials

Two-dimensional (2D) materials, in particular graphene and transition metal dichalcogenides (TMDC), have attracted great scientific interest over the last decade, revealing exceptional mechanical, electrical and optical properties. Owing to their layered nature, subnanometer-thick single-layer forms of these crystals can be chemically grown or mechanically isolated, representing an ultimately scaled-down platform for further miniaturization of electronic devices. Indeed, the large family of 2D materials contains hundreds of members, including metals, semiconductors, insulators, and others, covering the whole spectrum of potential applications. Availability of all necessary building blocks for the construction of all-2D solid-state devices makes this platform ideal for fabrication of ultrathin, transparent and flexible devices.

Extensively investigated graphene has demonstrated excellent electrical properties. However, the absence of a bandgap is an obstacle for its interaction with light and therefore limits applications in optics. In this aspect, atomically thin TMDC semiconductors appear to be an alternative, more promising platform, as they possess a direct band gap in the visible range in the monolayer form. Despite being only three atoms thick, these semiconductors demonstrate exceptionally large light absorption, efficient light emission, and strong light-matter interaction, attracting justified interest from the optics community. We will focus on their potential applications for optoelectronics in Chapter 4.

Even more, broken inversion symmetry and strong spin-orbit coupling in single-layer TMDC crystals reveal a new quantum number, the so-called valley index. Indeed, this unique degree of freedom of charge carriers is known for some materials since the 1970s. However, in the case of 2D semiconductors, spin-valley locking mechanism and valley contrasting optical selection rules open new ways for addressing, manipulation and sensing of this pseudospin, opening the whole new field of valleytronics. Due to the large splitting of the valence band, spin and valley degree of freedom become locked in these atomically thin materials. We employ this unique feature in Chapter 5 for indirect injection of spins into graphene by pumping valley polarized carriers in an adjacent TMDC monolayer. Being gapless, graphene does not allow direct optical injection of spins.

Another striking feature of 2D materials is their unique ability to be stacked in vertical heterostructures with strong electrical coupling between layers. The weak van der Waals force, which keeps components together, provides freedom in the assembly process, so that a lattice mismatch or a twist angle becomes unimportant in the first approximation. This provides a novel platform for harvesting complementary properties of the constituent materials, allowing the engineering of new artificial meta-materials as we demonstrate in Chapter 6. Furthermore, synergistic effects in van der Waals heterostructures enable completely new properties and phenomena, which do not exist in the single materials, with twist angle being an important knob for tuning these effects. We observe and exploit such novel phenomena arising in heterostructures of 2D semiconductors in the last chapter of this thesis.

On the way to the realization of practical optoelectronic and valleytronic applications, this thesis studies fundamental aspects of rich spin-valley physics of atomically thin semiconductors

Single-Layer MoS2 Electronics

Simone Bertolazzi, Andras Kis, Dominik Sebastian Lembke

CONSPECTUS: Atomic crystals of two-dimensional materials consisting of single sheets extracted from layered materials are gaining increasing attention. The most well-known material from this group is graphene, a single layer of graphite that can be extracted from the bulk material or grown on a suitable substrate. Its discovery has given rise to intense research effort culminating in the 2010 Nobel Prize in physics awarded to Andre Geim and Konstantin Novoselov. Graphene however represents only the proverbial tip of the iceberg, and increasing attention of researchers is now turning towards the veritable zoo of so-called "other 2D materials". They have properties complementary to graphene, which in its pristine form lacks a bandgap: MoS2, for example, is a semiconductor, while NbSe2 is a superconductor. They could hold the key to important practical applications and new scientific discoveries in the two-dimensional limit. This family of materials has been studied since the 1960s, but most of the research focused on their tribological applications: MoS2 is best known today as a high-performance dry lubricant for ultrahigh-vacuum applications and in car engines. The realization that single layers of MoS2 and related materials could also be used in functional electronic devices where they could offer advantages compared with silicon or graphene created a renewed interest in these materials. MoS2 is currently gaining the most attention because the material is easily available in the form of a mineral, molybdenite, but other 2D transition metal dichalcogenide (TMD) semiconductors are expected to have qualitatively similar properties.In this Account, we describe recent progress in the area of single-layer MoS2-based devices for electronic circuits. We will start with MoS2 transistors, which showed for the first time that devices based on MoS2 and related TMDs could have electrical properties on the same level as other, more established semiconducting materials. This allowed rapid progress in this area and was followed by demonstrations of basic digital circuits and transistors operating in the technologically relevant gigahertz range of frequencies, showing that the mobility of MoS2 and TMD materials is sufficiently high to allow device operation at such high frequencies.Monolayer MoS2 and other TMDs are also direct band gap semiconductors making them interesting for realizing optoelectronic devices. These range from simple phototransistors showing high sensitivity and low noise, to light emitting diodes and solar cells. All the electronic and optoelectronic properties of MoS2 and TMDs are accompanied by interesting mechanical properties with monolayer MoS2 being as stiff as steel and 30x stronger. This makes it especially interesting in the context of flexible electronics where it could combine the high degree of mechanical flexibility commonly associated with organic semiconductors with high levels of electrical performance. All these results show that MoS2 and TMDs are promising materials for electronic and optoelectronic applications.

2015

Large-Area Epitaxial Monolayer MoS2

Simone Bertolazzi, Ming-Wei Chen, Dumitru Dumcenco, Anna Fontcuberta i Morral, Marco Gibertini, Philippe Gillet, Andras Kis, Daria Krasnozhon, Yen-Cheng Kung, Oriol López Sánchez, Kolyo Marinov, Nicola Marzari, Dmitry Ovchinnikov, Aleksandra Radenovic

Two-dimensional semiconductors such as MoS2 are an emerging material family with wide-ranging potential applications in electronics, optoelectronics, and energy harvesting. Large-area growth methods are needed to open the way to applications. Control over lattice orientation during growth remains a challenge. This is needed to minimize or even avoid the formation of grain boundaries, detrimental to electrical, optical, and mechanical properties of MoS2 and other 2D semiconductors. Here, we report on the growth of high-quality monolayer MoS2 with control over lattice orientation. We show that the monolayer film is composed of coalescing single islands with limited numbers of lattice orientation due to an epitaxial growth mechanism. Optical absorbance spectra acquired over large areas show significant absorbance in the high-energy part of the spectrum, indicating that MoS2 could also be interesting for harvesting this region of the solar spectrum and fabrication of UV-sensitive photodetectors. Even though the interaction between the growth substrate and MoS2 is strong enough to induce lattice alignment via van der Waals interaction, we can easily transfer the grown material and fabricate devices. Local potential mapping along channels in field-effect transistors shows that the single-crystal MoS2 grains in our film are well connected, with interfaces that do not degrade the electrical conductivity. This is also confirmed by the relatively large and length-independent mobility in devices with a channel length reaching 80 mu m.

Amer Chemical Soc2015

Light Generation and Harvesting in a van der Waals Heterostructure

Esther Alarcon Llado, Andras Kis, Volodymyr Koman, Oriol López Sánchez, Aleksandra Radenovic

Two-dimensional (2D) materials are a new type of materials under intense study because of their interesting physical properties and wide range of potential applications from nanoelectronics to sensing and photonics. Monolayers of semiconducting transition metal dichalcogenides MoS2 or WSe2 have been proposed as promising channel materials for field-effect transistors. Their high mechanical flexibility, stability, and quality coupled with potentially inexpensive production methods offer potential advantages compared to organic and crystalline bulk semiconductors. Due to quantum mechanical confinement, the band gap in monolayer MoS2 is direct in nature, leading to a strong interaction with light that can be exploited for building phototransistors and ultrasensitive photodetectors. Here, we report on the realization of light-emitting diodes based on vertical heterojunctions composed of n-type monolayer MoS2 and p-type silicon. Careful interface engineering allows us to realize diodes showing rectification and light emission from the entire surface of the heterojunction. Electroluminescence spectra show clear signs of direct excitons related to the optical transitions between the conduction and valence bands. Our p-n diodes can also operate as solar cells, with typical external quantum efficiency exceeding 4%. Our work opens up the way to more sophisticated optoelectronic devices such as lasers and heterostructure solar cells based on hybrids of 2D semiconductors and silicon.

Amer Chemical Soc2014

Single-Layer MoS2 Electronics

Simone Bertolazzi, Andras Kis, Dominik Sebastian Lembke

2015