Passivating electron contact based on highly crystalline nanostructured silicon oxide layers for silicon solar cells

We present a novel passivating contact structure based on a nanostructured silicon-based layer. Traditional poly-Si junctions feature excellent junction characteristics but their optical absorption induces current losses when applied to the solar cell front side. Targeting enhanced transparency, the poly-Si layer is replaced with a mixed-phase silicon oxide/silicon layer. This mixed-phase layer consists of an amorphous SiOx matrix with incorporated Si filaments connecting one side of the layer to the other, and is referred to as nanocrystalline silicon oxide (nc-SiOx) layer. We investigate passivation quality, measured as saturation current density, and nanostructural changes, characterized by Raman spectroscopy and transmission electron microscopy, carefully studying the influence of annealing dwell temperature. Excellent surface passivation on n-type and also p-type wafers is shown. An optimum annealing temperature of 950 °C is found, resulting in a saturation current density of 8.8 fA cm2 and 11.0 fA cm2 for n-type and p-type wafers, respectively. Even before forming gas annealing, emitter saturation current densities of 27.9 fA cm2 (n+/n junction) and 32.0 fA cm2 (n+/p junction) are reached. Efficient current extraction is presented with specific contact resistivities of 86 mΩ cm2 on n-type wafer and 19 mΩ cm2 on p-type wafers, respectively. High-resolution transmission electron microscopy reveals that the layer stack consists of intermixed SiOx and Si phases with the Si phases being partly crystalline already in the as-deposited state. Thermal annealing at temperatures > 850 °C further promotes crystallization of the Si-rich regions. The addition of the SiOx phase enhances the thermal stability of the contact and should allow to tune the refractive index and improve transparency, while still providing efficient electrical transport through the crystalline Si phase, which extends throughout almost the entire contact.

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

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

Gizem Nogay

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.

EPFL2018

TEM characterization of textured silicon heterojunction solar cells

Christophe Ballif, Aïcha Hessler-Wyser, Christian Monachon

Increasing the efficiency of crystalline silicon (c-Si) solar cells requires the reduction of both bulk and interface recombination. Even if bulk recombination is almost suppressed, the symmetry of the crystal lattice is disturbed at the surface and hence, due in particular to non-saturated bonds (dangling bonds), a large density of defects exists. Thus, in this case, the free-carrier lifetimes are no longer limited by the quality of the bulk c-Si, but by its surface. To keep the recombination losses at the c-Si surface at minimal levels, the surface must be electronically well passivated. An efficient way to obtain passivation is to use low temperature grown (typically 200°C) hydrogenated amorphous silicon (a-Si:H) [1]. In the case of photovoltaic applications, the passivation of both c-Si wafer surfaces (i.e., the emitter and the rear surface) is of crucial importance for good performances. In this work, the 3-7 nm a-Si:H based passivation layers of the device are grown by VHF-PECVD in a single chamber. The solar cells consist of a multilayered structure: Al back contact / DC-sputtered ITO (Indium Tin Oxyde) / n/i a-Si:H back surface field (BSF) / n-type c-Si substrate with a resistivity of 1-3 Ωcm / intrinsic a-Si:H / i/p a-Si:H emitter / and a front contact made out of DC-sputtered ITO via a shadow mask to define the cells (diameter = 4.5 mm). Such devices are called heterojunction (HJ) silicon solar cells. Surface recombination losses are a major concern for all c-Si solar cells. In particular, mastering of HJ emitter and back surface field formation on textured c-Si is crucial for high-performance HJ solar cells. High Resolution Transmission Electron Microscopy (HRTEM) is necessary to identify the key microstructural features of the a-Si:H/c-Si interface, and TEM micrographs of HJ interfaces on flat and textured high-performance devices are shown for the first time and discussed with respect to the resulting solar cell electrical performances. TEM micrographs of our flat high-efficiency HJs show abrupt c-Si/a-Si:H/μc-Si:H interfaces for emitter and BSF formation. Whereas on the pyramidal facets of the textured substrate the growth is identical to the flat substrate interface, we observed unexpected epitaxial growth at the bottom of the pyramid valleys. We have identified these local epitaxial domains as an efficient surface recombination path, and by consequence, as responsible for the observed decreased VOC on textured HJ cells. When minimizing the density of epitaxial domains at the c-Si/a-Si:H interface by adapting the deposition conditions, a solar cell VOC of 660 mV is obtained. An additional modification of the textured c-Si surface morphology leads to VOCs as high as 700 mV.

Springer2008

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

Josua Andreas Stückelberger

EPFL2018

TEM characterization of textured silicon heterojunction solar cells

Christophe Ballif, Aïcha Hessler-Wyser, Christian Monachon

Springer2008

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

Gizem Nogay

EPFL2018