Optimization of front SiNx/ITO stacks for high-efficiency two-side contacted c-Si solar cells with co-annealed front and rear passivating contacts

In this contribution, we present an electron selective passivating contact metallised with a low temperature process to target front side applications in crystalline silicon (c-Si) solar cells. In addition to an interfacial silicon oxide (SiOx) and an in-situ phosphorous doped micro-crystalline silicon (μc-Si(n)) layer, it comprises an ultra-thin indium tin oxide (ITO) layer of 15 nm for lateral conductivity and a hydrogen rich silicon nitride (SiNx:H) layer which serves as hydrogen (H) reservoir and as anti-reflection coating. We use one single thermal treatment for 30 min at 350 °C to sinter the screen-printed paste, to recover sputtering damage induced during ITO deposition, and to diffuse hydrogen from the SiNx:H layer towards the c-Si/SiOx interface where it passivates interfacial defects. Applied to symmetrically processed textured samples, we find implied open-circuit voltage (iVOC) > 728 mV for optimal ITO thickness of 15 nm and annealing temperatures of 350 °C. The developed stack was applied on the front textured side of co-annealed (800 °C) p-type c-Si solar cells in combination with a tunnel oxide hole selective passivating contact on the rear side. We demonstrate solar cells with fill factor (FF) up to 81.9% and an open-circuit voltage (VOC) up to 719 mV. With a short-circuit current density (JSC) of 38.6 mA/cm2, we obtain a final cell efficiency to 22.8%. We find that the annealing of the SiNx:H/ITO stack strongly increases the ITO free carrier density penalizing the solar cell spectral response at high wavelengths.

Phosphorous-Doped Silicon Carbide as Front-Side Full-Area Passivating Contact for Double-Side Contacted c-Si Solar Cells

Christophe Ballif, Matthieu Despeisse, Luca Gnocchi, Franz-Josef Haug, Andrea Ingenito, Philipp Friedrich Hermann Löper, Gizem Nogay, Josua Andreas Stückelberger, Philippe Wyss

We present an electron selective passivating contact based on a tunneling SiOx capped with a phosphorous doped siliconcarbideandpreparedwithahigh-temperaturethermalanneal. We investigate in detail the effects of the preparation conditions of theSiCx(n)(i.e.,gasﬂowprecursorandannealingtemperature)on the interface recombination rate, dopant in-diffusion, and optical properties using test structures and solar cells. On test structures, our investigation reveals that the samples annealed at temperatures of 800–850 °C exhibit an increased surface passivation toward higher gas ﬂow ratio (r = CH4/(SiH4 + CH4)). On textured and planar samples, we obtained best implied open-circuit voltages (i-VOC) of 737 and 746 mV, respectively, with corresponding dark saturation current densities (J0) of∼8 and∼4 fA/cm2. The SiCx(n)layerswithdifferentrvalueswereappliedonthetextured front side of p-type c-Si solar cells in combination with a borondoped SiCx(p) as rear hole selective passivating contact. Our cell results show a tradeoff between VOC and short-circuit current density (JSC) dictated by the C-content in the front-side SiCx(n). On p-type wafers, best VOC = 706 mV, FF = 80.2%, and JSC = 38.0 mA/cm2 with a ﬁnal conversion efﬁciency of 21.5% are demonstrated for 2 × 2 cm 2 screen-printed cells, with a simple and patterning-free process based on plasma depositions and one annealing step 800 °C < T < 850 °C for the formation of both passivating contacts.

2018

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.