Optical Layers for Thin-film Silicon Solar Cells

In this work we develop and analyze optical layers for use in Micromorph solar cells, a tandem configuration with an amorphous silicon top cell and a microcrystalline silicon bottom cell. The morphology of the front electrode has a decisive role in maximizing the efficiency of a solar cell. To reach a better understanding of the requirements for the front electrode surface, we present a wide range of morphologies that can be obtained with as-grown rough zinc oxide (ZnO) and post-deposition argon plasma surface treatments. We correlate the morphological parameters to light scattering in transmission and reflection, and identify the inclination angles of ZnO pyramids as the most pertinent parameter for thin-film silicon solar cells. We show that there are no reflection losses at the interface between as-grown rough ZnO and silicon, and we quantify the reflection losses for smoother interfaces. With titanium dioxide, produced by reactive magnetron sputtering, we demonstrate that for flat interfaces reflection losses of up to 7.4% can be canceled at 550 nm wavelength. We show that in microcrystalline silicon cells p-type silicon sub-oxide (SiOx) can also be used to reduce reflection losses, and at the same time can act as field-creating window layer. We develop a wide range of mixed-phase SiOx layers and with energy-filtered transmission electron microscopy we reveal the filamentous nanostructure of films produced with high hydrogen dilution of the precursor gas mixture. A partial decoupling of electrical and optical parameters is achieved for such films, where the transparency and the refractive index are determined mostly by the silicon oxide matrix, while sufficient transverse conductivity for the use in solar cells is maintained by few-nanometer-wide silicon filaments. In thin-film silicon solar cells, p-type SiOx~0.5 shows the best results as a window layer with enhanced transparency, while strongly phosphorous-doped n-type SiOx~1 is best suited for use as an intermediate reflecting layer in tandem cells due to a low refractive index of 1.8 with sufficient transverse conductivity. The tunable resistance of doped SiOx layers can be used at various locations in a Micromorph cell to quench shunts or bad diodes in spatially non-uniform devices. Implementation of SiOx with these three functionalities in Micromorph cells has significantly contributed to increasing the best initial efficiency from 11.8% in 2006 to 13.5% in 2010. While rough ZnO front electrodes and SiOx-based intermediate reflecting layers both help to improve Micromorph cell efficiencies, they render the devices more sensitive to water-vapor-induced degradation. With lock-in thermography measurements we demonstrate that water contamination affects mainly the cell borders resulting in non-uniform distribution of the local open circuit voltage. Finally we show how free-carrier absorption and surface plasmon polariton absorption can reduce the reflectivity of the back reflector, and we present preliminary results aimed toward the realization of an absorption-free back reflector making use of polished ZnO and sputtered silver layers.

Low-Pressure Chemical Vapor Deposited Zinc Oxide Films

Laura Ding

Polycrystalline zinc oxide (ZnO) films, prepared by low-pressure chemical vapor deposition are investigated in this thesis. ZnO belongs to the class of transparent conductive oxide materials, as it is transparent to light from the visible to the near-infrared range and is simultaneously electrically conductive. These two properties allow ZnO films to be integrated in thin-film silicon solar cells, as well as other opto-electronic devices. In particular, thin-film solar cells require a contact layer covering the whole active layer in order to efficiently collect the photogenerated electrical current, and therefore, the film electrode at the front of the cell has to be a window to the sunlight, in addition to being able to transport current. ZnO’s electrical conductivity is usually improved by doping with impurities like boron, but the film transparency is reduced, and consequently, the current that the solar cell can produce decreases. Thus, the first point investigated in this thesis is to find ways to relax the trade-off between transparency and conductivity. Instead of doping, which increases the electron concentration, the electron mobility has to be improved. To do so, the electron transport is first studied and modeled for standard films, in order to better define and understand its limitations. Then, a new way of preparing ZnO bilayer films is shown to lead to enhanced transparency and light scattering, for a maintained conductivity compared to uniformly doped films. Alternatively, various treatments (hydrogen plasma, vacuum annealing and ultraviolet exposure) are tested, all of which reduce the density of defects that cause electron scattering in the ZnO; treated films present an improved conductivity and very high mobilities close to 60 cm2V−1s−1, which corresponds to the mobility value in single crystals of equivalent doping. In addition, these films absorb less than 2% of the visible-to-infrared light, which makes them very promising ultra-transparent electrodes, for solar cells or other applications. For use in thin-film silicon solar cells, two additional criteria have to be met besides trans- parency and conductivity. First, because the front electrode is also the substrate for the deposition of the rest of the cell layers, its surface morphology has to be favorable to the growth of silicon. Moreover, this surface has to present a rough texture capable of diffusing and trapping the light into the cell, and increasing its chance of being absorbed. These charac- teristics can be incompatible, but are nevertheless necessary to reach thin-film solar cells with high efficiencies. So, the second point of interest of this thesis is to adapt the surface of ZnO layers by investigating their preparation method. Combinations of different growth regimes in multilayers are proposed to enable a smoother controllable of the surface without resort to additional etching treatments, leading to improved solar cell electrical performance. Finally, the stability of ZnO films exposed to various conditions that modify their electrical and optical properties is investigated. First, ZnO is exposed to different oxidizing conditions (storage and annealing in air, exposure to moisture, plasma of carbon dioxide). The loss in conductivity from the interaction of the oxygen species with ZnO is characterized by a new infrared spectroscopic method and a hydrogen plasma treatment is investigated as a means to reverse or partially prevent the degradation in conductivity. Then, the effect of simulated sunlight exposure on ZnO film properties in solar cells is investigated. The resistivity of the front ZnO electrode decreases due to ultraviolet light absorption, and the resistivity of the back electrode increases due to the chemisorption of oxygen species, in absence of ultraviolet light. The front electrode transparency is also degraded; this effect is more pronounced for doped ZnO and its impact on the current photogeneration of solar cells is demonstrated. Therefore, a specific optimization of the front and back electrodes appears necessary. This thesis contributes on the one side to an in-depth understanding of the opto-electrical properties of ZnO films prepared by low-pressure chemical vapor deposition. On the other side, the different proposed approaches enable more flexibility in the development of more efficient and stable electrodes, not only for solar cells, but for many other applications such as electroluminescent diodes, flat-panel displays, touch-screens or transparent transistors.

EPFL2013

Transparent Passivating Contacts for Front Side Application in Crystalline Silicon Solar Cells

Josua Andreas Stückelberger

In this thesis, we present the development and characterization of novel approaches to carrier-selective passivating contacts for crystalline silicon (c-Si) solar cells. In our first approach, we benefit from a wide-bandgap material, namely mixed-phase silicon oxide (SiOx). High hydrogen dilution during the plasma-enhanced chemical vapor deposition of a SiOx layer leads to the growth of vertically oriented silicon filaments embedded in a silicon oxide matrix. The resulting mixed-phase material combines transparency and vertical conduction through the layer. We propose a layered contact structure starting with an ultra-thin chemically grown SiOx (~1.2 nm) at the c-Si wafer surface, followed by a phosphorus-doped bilayer of the mixed-phase SiOx, finishing with a nanocrystalline silicon layer that ensures contact with the metallization. With such a stack, an electron-selective passivating contact with a saturation current density J0 of 5.3 fA/cm2 is achieved on n-type wafers with hydrogenation, whereas on p-type wafers the contact reached 5.8 fA/cm2 even without hydrogenation. The contact is analyzed in detail with respect to its structure and its change upon thermal treatment. Two different growth regions are detected: one with the vertically oriented silicon inclusions and a second one in which the silicon phases have more lateral growth. Crystallization and atomic redistribution are analyzed during in-situ annealing in an electron microscope, leading to a better understanding of the change in distribution of phosphorus and oxygen as well as the nucleation sites. The influence of the annealing temperatures and dwell times as well as the initial doping concentration on the resulting in-diffused region and the passivation quality is reported. We use simulations to relate the influence of these parameters on passivation to the different recombination mechanisms. From the analyzed phosphorus doping profiles, an interesting observation is reported. The chemical oxide varies in thickness and density depending on the wafer polarity as well as the base resistivity. Proof-of-concept cells including this novel structure demonstrate the suitability for electron-selective passivating contacts at the device level with conversion efficiencies of 19.0% on planar wafers and 20.1% on textured wafers. Promisingly high short-circuit current densities (Jsc) of 35 mA/cm2 (40 mA/cm2) on planar (textured) with low parasitic absorption indicate its potential as a front contact in next-generation solar cells. Additionally, the beneficial feature of the smooth refractive index change within the layers that leads to a low reflectance over a broad wavelength range, similar to a built-in anti-reflection coating, is presented. A second approach to reach highly transparent electron-selective passivating contacts is demonstrated by the use of a plasma process based on the precursor gases phosphine (PH3), silicon tetrafluoride (SiF4), hydrogen (H2), and argon (Ar). The beneficial effect of fluorine in terms of passivation without the need for additional hydrogenation processes is shown, reaching implied open-circuit voltages of 730 mV on planar surfaces and 707 mV on textured surfaces. These layers are implemented in first proof-of-concept working devices with efficiencies of 19.5% on single-side-textured wafers and Jsc values of up to 40 mA/cm2.

EPFL2018

Novel Micromorph Solar Cell Structures for Efficient Light Trapping and High-Quality Absorber Layers

Mathieu Gérard Boccard

Key elements involved in the fabrication of Micromorph thin-film silicon solar cells, a tandem device including an amorphous silicon top cell and a microcrystalline silicon bottom cell, are studied in this manuscript. Due to the very short diffusion lengths of photogenerated carriers in both materials, the photoactive layers of both sub-cells of Micromorph devices must be kept thin enough to ensure carrier collection. Due to this limited thickness, not all valuable light (i.e. light of higher energy than the band-gap) can be fully absorbed after one pass through the absorber layers. Advanced light-harvesting schemes are thus mandatory to achieve high conversion efficiencies. Random rough interfaces are typically used to induce light scattering in the photoactive layers, thus elongating the light path through these layers, enhancing their absorption. A simple and analytical way of modeling light harvesting in thin-film solar cells is developed. Its validity is demonstrated by comparing with experimental measurements involving different types of rough interfaces. It is shown that present light-scattering schemes come close to the best theoretically achievable scattering from random rough interfaces. With the morphology of a state-of-the-art rough ZnO layer, 32mA/cm2 can be obtained for a 1-μm-thick μc-Si:H layer, compared to 33.2 mA/cm2 for the Yablonovitch limit. Most of the gains in terms of light management are therefore to be made by making non-active layers more transparent (since these layers are presently responsible of ∼ 7 mA/cm2 of losses for a 1-μm-thick μc -Si:H layer). Parasitic absorption in non-active layers is also shown to be equally detrimental on both sides of the cell in the infrared part of the spectrum, corresponding to the wavelength range for which light trapping is most important. To improve significantly light trapping, complementary strategies to random rough interfaces must therefore be applied. For such a strategy, part of the light has to be prevented to escape from the cell. This can be obtained for example by using an angular filter, transmitting all light up to a certain incidence angle, and reflecting all light of higher incidence angle. An experimental optical setup based on spatial filtering is presented. It is shown to prevent 80% of light from escaping the cell, additionally to other light trapping strategies. A strong absorption enhancement of the complete device is demonstrated, at the cost of a reduction of the acceptance angle. However, most of the spared light is shown to be absorbed in non-active layers. A drastic reduction of parasitic absorption from these layers is therefore identified as a prerequisite to benefit from a better light trapping. Turning then to complete device analysis, the requirements of the front electrode for high- efficiency Micromorph devices are discussed point-by-point, focusing both on optical and electrical requirements. The need for sharp and relatively small features for an efficient coupling of light in the top cell is notably pointed out, as well as the need for features large enough to scatter light of wavelength up to 1100 nm for a high bottom cell current. The impact of sharp and large features on the electrical performances of the cells is also underlined. An optimal morphology is proposed, exhibiting features that are the smallest enabling scattering of light up to 1100 nm, and the sharpest that do not harm the electrical quality of the bottom cell. A device with a stable efficiency of 11.8% could be obtained on such a substrate. To avoid this trade-off, the combination of features with different sizes in a multi-scale elec- trode architecture is studied. It is shown that even though no gain in terms of light scattering is seen compared to a state-of-the-art single-scale morphology, a better electrical quality can be obtained, making the multi-scale approach of interest. A noteworthy 14.1% initial efficiency is demonstrated with such an architecture, with a short-circuit current density of 14 mA/cm2 for a total thickness of the silicon layers of 3 μm. Another way to add a degree of freedom in the design of a Micromorph device is also presented, employing a smoothening intermediate layer between both sub-cells. A separate tuning of the morphology inducing light scattering in each sub-cell can be made. Several routes are explored, out of which promising results are obtained by using a spin-coated lacquer on the top cell. A slight etching uncaps the tips of the top cell surface and allow for electrical conduction, whereas the smoothening effect is preserved. A large top cell current boost (up to+2.5mA/cm2)andopen-circuitvoltageimprovement(+50mV)areobtained,withmany adjustable processing parameters to obtain various morphologies. The newly developed concepts enable a better understanding of the present limitations of Micromorph devices. We believe that, by implementing these concepts in Micromorph tandem devices employing state-of-the-art amorphous and microcrystalline single-junction solar cells, stable 13.5% to 14% efficiency are within reach. Yet, increasing further the efficiency of Micromorph devices will likely require material improvements.

EPFL2012