Functional properties of III-V nanowires addressed by Raman spectroscopy

In recent years, semiconductor nanowires have attracted considerable attention as a result of their unique properties and potential applications in many fields. In particular, they can be very attractive materials for certain optoelectronic and electronic devices, such as lasers, detectors and solar cells, which benefit from the photonic properties of nanowires. In order for these future technologies to become a reality, a good understanding of the functional properties of nanowires is fundamental. In this thesis we have investigated the optical and the electrical properties of III-V semiconductors nanowires by the means of Raman spectroscopy. Thanks to its non-destructive and spatial resolution, Raman spectroscopy is a powerful contact-less tool for the characterization of semiconductor nanowires. Raman spectroscopy can provide information about crystallinity, orientation, size and chemical composition. In polar semiconductors it is also possible to characterize the free carriers, through the coupling of plasmons with longitudinal optical modes. Due to the small size and particular morphology of nanowires, the interaction of light can be more complex than in thin films. In particular, the existence of photonic modes alters significantly the corresponding light-matter interaction. In this thesis we exploit the use of photonic modes for the compositional mapping of nanowire core-shell heterostructures and also to circumvent the macroscopic selection rules. In the first part of this thesis, we have performed Raman scattering measurements on GaAs/AlGaAs core/shell nanowires. We have shown that it is possible to select and characterize regions of the structure with different Aluminum content, by performing the measurements at different laser wavelengths. Then, we have shown that the photonic modes can be modified by suspending the nanowires on a trench. We have shown that in this case it is possible to enhance the response of the longitudinal optical phonon mode. We have then applied this configuration for the characterization of the hole concentration on p-type GaAs nanowires in back-scattering geometry. The second part of the thesis focused on the assessment of free carriers by Raman spectroscopy in systems with an expected high electron mobility: GaAs nanowires with a modulation doped structure and InAs(Sb) nanowires. Raman measurements were performed as a function of the temperature on modulation doped GaAs/AlGaAs nanowire. By characterizing the coupling between free carrier and the LO phonons, we have extracted the concentration and the mobility of carriers. We have found that Si donors are almost ionized for a temperature above 50 K. We have shown that the mobility is limited by interface scattering, with values of 400 cm^2/Vs at room temperature and 2700 cm^2/Vs at low temperature. Finally, we investigated the electronic properties of InAs(Sb) nanowires as a function of the temperature. The effect of a dielectric coating on the electronic properties was also studied. We have found an increase of mobility and electron concentration with the antimony content , moving from 5100 cm^2/Vs for InAs nanowires, to 17500 cm^2/Vs for InAsSb with 35% of antimony at 14K. Moreover, we have shown that in the case of InAs electrons are located in the accumulation layer at the surface, while for InAsSb our measurements are consistent with the carriers located in the nanowire core.

Spin-valley optoelectronics based on two-dimensional materials

Dmitrii Unuchek

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

EPFL2019

III-V nanowire arrays: growth and light interaction

Esther Alarcon Llado, Sonia Conesa Boj, Anna Dalmau Mallorquí, Martin Heiss, Federico Matteini, Eleonora Russo

Semiconductor nanowire arrays are reproducible and rational platforms for the realization of high performing designs of light emitting diodes and photovoltaic devices. In this paper we present an overview of the growth challenges of III-V nanowire arrays obtained by molecular beam epitaxy and the design of III-V nanowire arrays on silicon for solar cells. While InAs tends to grow in a relatively straightforward manner on patterned (111) Si substrates, GaAs nanowires remain more challenging; success depends on the cleaning steps, annealing procedure, pattern design and mask thickness. Nanowire arrays might also be used for next generation solar cells. We discuss the photonic effects derived from the vertical configuration of nanowires standing on a substrate and how these are beneficial for photovoltaics. Finally, due to the special interaction of light with standing nanowires we also show that the Raman scattering properties of standing nanowires are modified. This result is important for fundamental studies on the structural and functional properties of nanowires.

Institute of Physics2014

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

Spin-valley optoelectronics based on two-dimensional materials

Dmitrii Unuchek

EPFL2019