Full-Area Passivating Contacts with High and Low Thermal Budgets: Solutions for High Efficiency c-Si Solar Cells

Today more than 90% of the global PV market is covered by c-Si solar cells which are limited by recombination losses at the metal-semiconductor interface. This recombination path can be avoided by separating the metal from the c-Si wafer by introducing a buffer layer that passivates electronically the wafer surface while still allowing the flow of one type of carrier. Such structures are called carrier selective passivating contacts. In the scope of this thesis, carrier selective passivating contacts with low and high thermal budgets are investigated with the purpose of achieving a good understanding of the junction formation, the working principle, limiting factors, and integration requirements. Silicon heterojunction (SHJ) solar cells are studied as representatives for solar cells processed with low thermal budget. Solar cells with interfacial oxide contacts are investigated as the cell concept for high thermal budgets. To be industrially relevant, contact formation of the latter is studied with p-type wafers. The carrier selective passivating contacts based on microcrystalline silicon (mc-Si:H) are studied for SHJ solar cells with low thermal budget. It is demonstrated that mc-Si:H layers improve the optical and electrical performance of the SHJ solar cells compared to cells with purely amorphous contacts. However, as the layer crystallinity increases with thickness, a trade¿off between short circuit current density and fill factor is encountered. By combining a MoOx front hole-contact and a mc-Si:H(n) rear electron-contact, this trade¿off is avoided. Applying an electrodeposited copper front metallization, a short circuit current density of 38.9 mA/cm2 and a fill factor of to 80% are obtained leading to an efficiency of 22.5%. The passivating hole contacts with high thermal budget are developed using a chemically grown oxide (SiOx) and boron doped silicon-carbide which is deposited under Si-rich conditions by plasma enhanced chemical vapour deposition. It is observed that introducing an undoped Si inter¿layer between SiOx and SiCx(p) is necessary to prevent chemical reaction between carbon atoms in the SiCx(p) and the adjacent SiOx, and consequently to obtain wellpassivated SiOx/c-Si interface. With this contact structure, an implied open circuit voltage value of 718 mV and a specific contact resistivity value of 17m cm2 are attained. The contact structure is tested at device level by realizing proof-of-concept hybrid solar cells that feature a high thermal budget rear hole-contact and a low thermal budget SHJ front electron-contact. With this concept, the fill factor of 81.8% is attained. In an effort to improve the hole-contact property further, in-situ incorporation of fluorine into the boron-doped hole-contact is explored. It is observed that in the as-deposited state, fluorine is evenly distributed within the contact layer of SiCx:F(p). Upon annealing, fluorine diffuses toward the c-Si wafer and accumulates at the interface where it reduces the defect states. With this contact structure, implied open circuit voltage values up to 735mV are achieved. The potential of the fluorinated hole-contact is investigated at device level by realizing both sides-contacted co-processed solar. For this purpose in-situ phosphorous doped SiCx(n) layers were developed as a front contact. Planar, both sides-contacted p-type solar cells attain an impressive fill factor value of 84% and an open circuit voltage of 727 mV.

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

Single and multi-junction thin film silicon solar cells for flexible photovoltaics

Thomas Söderström

This thesis investigates amorphous (a-Si:H) and microcrystalline (μc-Si:H) solar cells deposited by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) in the n-i-p or substrate configuration. It focuses on processes that allow the use of non transparent and flexible substrates such as plastic foil with Tg < 180°C like poly-ethylene-naphtalate (PEN). In the first part of the work, we concentrate on the light trapping properties of a variety of device configurations. One original test structure consists of n-i-p solar cells deposited directly on glass covered with low pressure chemical vapour deposition (LP-CVD) ZnO. For this device, silver is deposited below the LP-CVD ZnO or white paint is applied at the back of the substrate as back reflector. This avoids the parasitic plasmonic absorptions in the back reflectors, which are observed for conventional rough metallic back contacts. Furthermore, the size and morphology of the LP-CVD ZnO is varied and the relation between the substrate morphology and the short circuit current density (Jsc) is experimentally explored. As a result, the Jsc can be increased by 23% for a-Si:H and 28% for μc-Si:H solar cells compared to the case of flat substrate and the role of the size and shape can be clearly separated. We also explore the optical behavior of single and multi-junction devices prepared with different back and front contacts. The back contact consists either of a 2D periodic grid with moderate slope, or of LP-CVD ZnO with random pyramids of various sizes. The front contacts are either a 70 nm thick, nominally flat ITO or a rough 2 microns thick LP-CVD ZnO. We observe that, for a-Si:H, the cell performance is critically dependent on the combination of thin flat or thick rough front TCOs and the back contact. Indeed, for a-Si:H, a thick LP-CVD ZnO front contact provides more light trapping on the 2D periodic substrate. The Jsc relatively increases by 7 % with LP-CVD ZnO compared to ITO. Then, we study the influence of the thick and thin TCOs in conjunction with thick absorbers like triple junction or mc-Si:H solar cells. Because of the different nature of the optical systems, thick (> 1 micron) against thin (

University of Neuchâtel2009

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