Semiconductors based on group IV elements are widely used in the fields of micro-electronics, optics and photonics. The group IV alloys are processed using plasma enhanced chemical vapor deposition and its opto-electrical properties are a result of the material composition and structure. Infrared and Raman spectroscopy are complementary and powerful tools for providing these essential material characteristics. In this work, the vibrational modes present in hydrogenated, oxygenated and carbonated group IV alloys are investigated in a unique range of amorphous and nano-crystalline Si_X≥0Ge_1−X:H films and their alloys with C, O and Sn. Measurements are performed both post-deposition and following extended exposure to the ambient and de-ionized water. This comprehensive review is of value in the fields of material science and engineering as a single work of reference for group IV peak identification. Additionally, the effect of electrical screening, the influence of the dielectric medium on the peak frequency of a vibrational mode, is illustrated using the experimentally observed frequency shifts of X-O and X-H (X = C, Si, Ge) vibrational modes. All experimentally observed center frequencies of silicon hydride stretching modes in silicon solids and corresponding silicon-hydride configurations are identified using a straightforward Lorentz-Lorenz model approximation and considering all potential hydrogenated volume deficiencies within a tetrahedrally coordinated amorphous and nanocrystalline lattice. It shows that the stretching mode signature can reveal detailed information on the volume deficiencies in IV-valence alloys.

Amorphous and nano-crystalline germanium is of potential interest for a wide range of electronic, optical, opto-electronic and photovoltaic applications. In this work the influence of deposition temperature on hydrogenated germanium (Ge:H) films was characterized, using over 200 Ge:H and over 70 SiGe:H films. The demonstrated temperature-induced densification of Ge:H films resulted in more stable films with a lower bandgap energy and dark conductivity and higher activation energy.

A logical next step for achieving a cost price reduction per Watt peak of photovoltaics (PV) is multijunction PV devices. In two-terminal multijunction PV devices, the photo-current generated in each subcell should be matched. Intermediate reflective layers (IRLs) are widely employed in multijunction devices to increase reflection at the interface between subcells to enhance current generation in the subcell(s) positioned before the IRL, in reference to the incident light. In this work, the results of over 65 multijunction devices are presented, in order to explore the effect of different current matching approaches. The influence of variations in absorber thickness as well as thickness variations of different IRLs based on silicon-oxide, various transparent conductive oxides (TCO), and metallic layers on all-silicon multijunction PV devices is studied. Specifically, hybrid, 2-terminal, monolithically integrated silicon heterojunction (SHJ) and thin film nanocrystalline silicon (nc-Si:H) and amorphous silicon (a-Si:H) tandem and triple junction devices are processed. Based on these experiments, certain design rules for optimal current matching operation in multijunction devices are formulated. Finally, taking these design rules into account, record all-silicon multijunction devices are processed. Conversion efficiencies close 15% and (Formula presented.) V are demonstrated for triple junction SHJ/nc-Si:H/a-Si:H devices. Such conversion efficiencies for a wireless, high-voltage wafer-based all-silicon 2-terminal multijunction PV device opens the way for efficient autonomous solar-to-fuel synthesis systems as well as other wireless innovative approaches in which the multijunction solar cell is used not only as a photovoltaic current-voltage generator, but also as an ion-exchange membrane, electrochemical catalysts, and/or optical transmittance filter.

In this paper the opto-electrical nature of hydrogenated group IV alloys with optical bandgap energies ranging from 1.0 eV up to 2.3 eV are studied. The fundamental physical principles that determine the relation between the bandgap and the structural characteristics such as material density, elemental composition, void fraction and crystalline phase fraction are revealed. Next, the fundamental physical principles that determine the relation between the bandgap and electrical properties such as the dark conductivity, activation energy, and photoresponse are discussed. The unique wide range of IV valence alloys helps to understand the nature of amorphous (a-) and nanocrystalline (nc-) hydrogenated (:H) germanium films with respect to the intrinsicity, chemical stability, and photoresponse. These insights resulted in the discovery of i) a processing window that results in chemically stable Ge:H films with the lowest reported dark conductivity values down to 4.6·10^-4 (Ω ·cm)^-1 for chemical vapor deposited Ge:H films, and ii) O, C and Sn alloying approaches to improve the photoresponse and chemical stability of the a/nc-Ge:H alloys.

In this abstract an overview is presented of research performed in the DISCO project, on the development of a silicon-based high voltage multijunction device for autonomous solar to fuel applications.'

Crystalline silicon tandem devices with perovskites, CIGS, and nanocrystalline silicon, as well as the TOPCon design, are incompatible with the conventional pyramidal surface texture of silicon. This is a result of crack formation in nano to polycrystalline growth on large sharp surface features. In this work, three texturing approaches are investigated, using alkaline and/or acidic wet chemical etches, that can lead to the crack-free growth of nano to polycrystalline materials on textured surfaces. In this work, we show that without acidic smoothening, the fraction of <111> pyramidal surface coverage has to remain relatively small to prevent crack formation during crystalline growth on these surfaces. Applying an acidic etch as a function of time continuously smoothens surface features. This shifts the reflection to wider scattering angles and results in higher total reflected intensity with respect to the conventional texture, making it an interesting option for a wide variety of tandem pv applications. Finally, we demonstrate crater-like features on a <100> monocrystalline silicon surface using an etching process including a sacrificial layer. These craters increase light scattering into wider angles, but to a lesser extent than the former approach. In terms of passivation, we demonstrate the positive effect of a post deposition hydrogen treatment. Initial dilution of the silane plasma improves passivation on a <111> surface, but is detrimental to passivation on a <100> surface, likely because the hydrogen dilution results in epitaxial growth at the c-Si/a-Si:H hetero-interface. A minority carrier lifetime of over 3 ms has been achieved for all texturing approaches, after deposition of a 15 nm a-Si:H layer on both sides of the wafer, for different a-Si:H deposition and annealing schemes.

Low-cost multijunction photovoltaic devices are the next step in the solar energy revolution. Adding a bottom junction with a low bandgap energy material through plasma enhanced chemical vapor deposition (PECVD) processing could potentially provide a low-cost boost in conversion efficiency. A logical candidate for this low bandgap material is germanium. In this work we investigate the growth of PECVD processed hydrogenated amorphous/nano-crystalline germanium (a/nc-Ge:H), by characterizing over 100 samples, processed with a wide range of deposition pressures, powers, temperatures and GeH₄ dilution in hydrogen, using elemental analysis, vibrational analysis and analysis of the opto-electrical properties. We have identified a small processing window in which nc-Ge:H films are processed reproducibly. We also report on the strong correlation between the refractive index of the films and the presence- and extent of post-deposition oxidation. Notably, the oxidation generally increased the photoresponse of the films, as it results in a decrease of room temperature σ_d by 1-3 orders of magnitude. However, oxidation results in an increase of the bandgap energy and therefore impedes the development of a low bandgap material. The lowest E₀₄ we report is about 1.1eV, with an E_Tauc of 0.9eV and an σ_ph/σ_d of 3.4.

Crystalline silicon tandems with perovskites, CIGS and nanocrystalline silicon, as well as the TOPcon design are incompatible with the conventional pyramidal surface texture of silicon. Three texturing approaches, using alkaline and/or acidic wet chemical etches, are investigated in this work, that can lead to the crack-free growth of a nano- to poly-crystalline silicon material on textured surfaces. Without acidic smoothening, the fraction of <111> pyramidal surface coverage has to remain relatively small to prevent crack formation during crystalline growth. Applying an acidic etch as a function of time continuously smoothens surface features. This shifts the reflection to wider scattering angles and results in higher total reflected intensity with respect to the conventional texture, making it an interesting option for a wide variety of tandem pv applications. Finally we demonstrate crater like features on a <100> monocrystalline silicon surface using an etching process inlcuding a sacrificial layer. These craters increases light scattering into wider angles, but to a lesser extent than the former approach.

Tandem photovoltaic (PV) devices are receiving a lot of attention as the next step in PV for further increasing performance in combination with reducing the cost price per Watt peak. The integration of an effective tunnel recombination junction (TRJ) is crucial for efficient multijunction performance. In this work a rigorous and extensive study is presented that reveals the fundamental operating mechanisms that govern the TRJ performance. This is achieved by performing a structural study on the TRJ design in multiple tandem architectures based on different photovoltaic absorber layers. Experimental results are presented of a large number of tandem devices, including SHJ/nc-Si:H, nc-Si:H/a-Si:H, nc-Si:H/a-SiGe:H and a-SiGe:H/a-Si:H, in which the same p-layer design variations are applied. Across these device architectures the influence of the p-layer material properties, p-layer thickness, bilayer configurations and p-doped contact layer properties are investigated, to yield a unique insight into TRJ behavior.

Bandgap energy profiling is applied in a variety of materials for photovoltaic technologies, such as chalcogenides, III–V materials and perovskites. Bandgap profiling of the absorber layer is used to fight the fundamental loss mechanisms imposed by the bandgap energy of the absorber for the maximum voltage and current that a photovoltaic device can generate. The bandgap profile can be affected by a number of profiling strategies, such as the difference between the maximum and minimum bandgap energy, the position of the minimum bandgap energy, the width over which this minimum bandgap energy occurs and the total absorber width. These parameters have a complex effect on output characteristics of a photovoltaic device. Varying multiple parameters at once further increases the complexity, limiting the effectiveness of rigorous physical opto-electrical modelling. In this work we therefore present an expedient semi-empirical approach for the optimal bandgap profiling of stoichiometric absorbers. Using PECVD processed amorphous silicon germanium as a model, we present a unique set of semi-empirical relations that simulate the V_OC and J_SC of solar cells as a function of the bandgap energy profile. For this model, the influence of deposition conditions such as the relative germane flow rate, the deposition power and substrate temperature on the opto-electrical properties of a-SiGe:H films is first characterized. Opting for the relative germane flow rate to control the bandgap profiling, the experimental results of a large number of solar cells with profiled a-SiGe:H absorber are presented, varying: 1. the absorber thickness, 2. the peak germane flow rate, so minimum bandgap energy, and 3. the introduction of a plateau at the minimum bandgap energy. Using this experimental data and optical simulations, the expedience and effectiveness of the semi-empirical approach is demonstrated.

Doped hydrogenated silicon oxide layers (SiO_X:H) have recently been successfully integrated as front window layers, back reflector layers, intermediate reflector layers, passivation layers, and junction layers in thin-film silicon solar cells. Depending on the deposition conditions of the SiO_X:H layers, some devices suffer from a degradation in performance in time. In this paper, we demonstrate the responsible mechanism involved. It is demonstrated that oxidation of the p-Type doped (p-)SiO_X:H with a high crystallinity and, therefore, poor passivation of crystalline grains is responsible for this degradation. The oxidation of p-SiO_X:H is caused by the in-diffusion of water vapor from the ambient air. Stable p-SiO_X:H can be obtained if the material is processed at higher pressure. In addition, the degradation can be prevented if the cell is well encapsulated, like using dense n-Type (n-)SiO_X:H in the back reflector of the cell.