Nanoscale Growth Initiation as a Pathway to Improve the Earth-Abundant Absorber Zinc Phosphide

Growth approaches that limit the interface area between layers to nanoscale regions are emerging as a promising pathway to limit the interface defect formation due to mismatching lattice parameters or thermal expansion coefficient. Interfacial defect mitigation is of great interest in photovoltaics as it opens up more material combinations for use in devices. Herein, an overview of the vapor-liquid-solid and selective area epitaxy growth approaches applied to zinc phosphide (Zn3P2), an earth-abundant absorber material, is presented. First, we show how different morphologies, including nanowires, nanopyramids, and thin films, can be achieved by tuning the growth conditions and growth mechanisms. The growth conditions are also shown to greatly impact the defect structure and composition of the grown material, which can vary considerably from the ideal stoichiometry (Zn3P2). Finally, the functional properties are characterized. The direct band gap could accurately be determined at 1.50 +/- 0.1 eV, and through complementary density functional theory calculations, we can identify a range of higher-order band gap transitions observed through valence electron energy loss spectroscopy and cathodoluminescence. Furthermore, we outline the formation of rotated domains inside of the material, which are a potential origin of defect transitions that have been long observed in zinc phosphide but not yet explained. The basic understanding provided reinvigorates the potential use of earth-abundant II-V semiconductors in photovoltaic technology. Moreover, the transferrable nanoscale growth approaches have the potential to be applied to other material systems, as they mitigate the constraints of substrate-material combinations causing interface defects.

High coupling materials for thin film bulk acoustic wave resonators

Janine Conde

Radio frequency (RF) filters based on bulk acoustic wave resonances in piezoelectric thin films have become indispensable components in mobile communications. The currently used material, AlN, exhibits many excellent properties for this purpose. However, its bandwidth is often a limiting factor. In addition, no tuning is possible with AlN. Ferroelectrics would offer both larger coupling to achieve larger bandwidths, and tunability. However, their acoustic properties are not well known, especially in the thin film case. The goal of this thesis is to investigate the potential and identify the limitations of ferroelectric thin films for thickness mode resonators in the 0.5 - 2 GHz range. The Pb(Zrx,Ti1-x)O3 (PZT) solid solution system is the main candidate, since it is known for its large piezoelectric constants and its growth is already well studied. As a main test vehicle, free standing thin film bulk acoustic resonator (TFBAR) structures with Pt/PZT/Pt/SiO2 membranes were successfully fabricated using silicon micro-machining techniques. The main drawback of ferroelectrics is the damping of acoustic waves by domain wall motion both in the RF electric field and in the pressure wave. For this reason films with varying orientations and compositions were investigated. From the device structures the electro-mechanical coupling constants kt2, the quality factors (Q-factors) and several materials parameters have been obtained. High coupling constants have been found for sol-gel Pb(Zr0.53,Ti0.47)O3 films with a {100} texture, kt2 is found to be 0.4 for a 1 µm thick film and 0.8 for a 3.8 µm thick film. However, the Q-factors of these films are low, 18 for the first film and 3 for the second film. The increase of kt2 and the decrease of the Q-factor with frequency indicates that the domains present in these films contribute to these characteristic parameters. It was generally observed that high coupling constant are associated to low Q-factors. This became evident when comparing films with 53/47 composition, where both tetragonal and rhombohedral phases are present, to tetragonal films as well as when comparing {100} textures with (111) textures. Both for the 53/47 composition and for the {100} texture, ferroelastic domain walls are thought to play a bigger role than for tetragonal compositions and (111) textures. The highest figure of merit (FOM) of about 15 was found when combining the composition leading to a high coupling constant (53/47) and the orientation leading to lower losses (111). However the losses even in this film are too high for RF-filter applications. On the other hand, films with low Q-factors but high coupling could prove very useful as transducers for ultrasonic imaging applications, where low Q-factors are desired. The stiffness coefficients of the studied PZT films were shown to be higher than expected from ceramics data. Most likely the stiffness of ceramics always contains domain contributions leading to softening. In contrast, in textured films the variety of domain orientation is very much reduced. In order to reduce losses due the presence of ferroelastic domains three different potential solutions were explored. The first idea was to manipulate the domain populations of the films deposited on silicon by using heat and vacuum treatments. Silicon substrates are known from previous works to be unfavourable for high c-domain fractions. It was discovered that an anneal in vacuum at 550 °C lead to a significant reduction of c-domains in tetragonal 30/70 PZT ({100}). On the contrary, if the sample was subjected to a compressive stress during cooling, the c-domain fraction could be increased. Analysis of the film stress versus temperature curves revealed a trend consistent with theoretical predictions, i.e. a phase boundary between the c/a/c/a and the a1/a2/a1/a2 domain patterns between room temperature and the Curie temperature θC. However, even though this method reveals interesting results, it can not be exploited as a method to achieve a sufficient c-domain population. The second idea explored was the implementation of a high thermal expansion material as a substrate. PZT films deposited on MgO are known to be compressive due to the difference in thermal expansion of the two materials. The compressive stress leads to highly c-axis oriented PZT films. Devices using MgO substrates were fabricated, however difficulties in the micro-machining of the MgO substrate inhibited a complete liberation of the membrane. Nevertheless, preliminary measurements indicate these devices could lead to both high coupling and high Q-factors, suggesting that further detailed study of this method is worthwhile. As a third method for avoiding ferroelastic domains, the uniaxial ferroelectric potassium lithium niobate (KLN) was explored. The unique ferroelectric axis in this material means that only 180° domain walls are present, which can theoretically be removed by poling. This material has been deposited in thin film form using pulsed laser deposition (PLD). KLN thin films with a {001} texture were deposited successfully on Pt/Si substrates. The films were piezoelectric with a d33,f value of around 10 pm/V and a dielectric constant of 250. This is the first time that piezoelectric properties were measured on KLN thin films. A columnar structure has been observed, however the small grain size and the rough surface currently make it difficult to apply this material to TFBAR's.

EPFL2009

Fabrication and Characterization of Functional ALD Metal Oxide Thin Films for Solar Applications

Ludmilla Steier

Motivated to revolutionize our today's fossil fuels based energy production, my work concentrated on the investigation of promising low-cost materials for photoelectrochemical hydrogen production and photovoltaic electricity generation. Hydrogen presents a fully scalable energy storage solution while photovoltaics have the biggest potential for clean electricity generation. Both are combined in the hydrogen-based economy that will be introduced in Chapter 1. A clear way to achieve this revolutionary technological and societal goal is through fundamental understanding of the complex electronic properties of the most promising low-cost semiconductors offering strong visible light absorption. The modern fields of photoelectrochemical (PEC) water splitting and photovoltaics have a lot in common: materials, scientific concepts and theoretical background. In other words, their complementarity was a strong motivation for the interdisciplinary work presented in this thesis. The main focus in this thesis is on hematite, which is a promising low-cost material offering visible light absorption and the chemical robustness for photoelectrochemical water oxidation. However, it has two major drawbacks: firstly, for a semiconductor, hematite has extremely low electron and hole mobilities. This makes it challenging to collect charges that are photo-generated deep within the hematite layer and far away from the surface. Secondly, water oxidation appears to be limited by trap states located in the mid band gap region. Chapter 3 addresses these drawbacks showing that doping of hematite from the underlayer, surface passivation from annealing treatments and/or overlayers are all key parameters to consider for the design of more efficient iron oxide electrodes. By better understanding the underlying principles of over- and underlayers, I was able to design multilayered hematite photoanodes comprised of functional thin films to obtain a significant reduction in the water oxidation overpotential. Whereas hematite thin film electrodes were fabricated by ultrasonic spray pyrolysis in Chapter 3, I introduce a new atomic layer deposition (ALD) route towards crystalline, highly photoactive, phase pure and impurity-free hematite films in Chapter 4. With this thin film model system I could precisely demonstrate that only the 10 nm thick space charge region of hematite is photoactive, which presents a major challenge when considering that around 60-70 nm are needed to achieve sufficient light absorption as shown in Chapter 5. In light of this charge transport limitation, I propose and demonstrate new host-guest electrode designs that would be indispensible for the realization of high performance ALD hematite photoanodes. To complement these studies, I demonstrate in Chapter 5 the basis for an optoelectronic modeling of the hematite PEC device that helps identifying and eliminating major optical and electronic losses in the PEC cell. In Chapter 6 my work on ALD SnO2 as an electron selective layer (ESL) led to major advances in low-cost flat hybrid organic-inorganic perovskite solar cells. The tin oxide layer is found to resolve the problem of an energy band misalignment encountered with the previously used ALD TiO2 ESL in addition to stabilizing the photovoltaic performance. Hysteresis-free solar conversion efficiencies of up to 18% have been achieved for flat devices paving the way towards low-cost flat film perovskite solar cells that will easily surpass the photovoltaic performance of polycrystalline silicon solar cells in the near future.

EPFL2016

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