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Poly-Si Passivating Contacts Hydrogenation by Microwave Annealing
Hydrogenation is a crucial step in the fabrication of high-efficiency silicon solar cells. In this study, we demonstrate the for the first time effectiveness of hydrogen activation via microwave annealing of hydrogen-rich dielectrics coated on poly-Si passivating contacts. This method is compared with conventional hydrogenation techniques, such as annealing in N2 in the presence of a hydrogen-rich source (such as hydrogenated aluminum oxide (AlOx:H), hydrogenated silicon nitride (SiNy:H), or a AlOx:H/SiNy:H stack). Key improvements observed include a reduction in J0 from 30 to <5 fA/cm2, an increase in iVoc from 690 to >730 mV, and an enhancement in effective lifetime (teff) from 0.6 to ~3.5 milliseconds on phosphorus-doped poly-Si/SiO2 passivating contact samples. With a very short annealing time of ~1-2 minutes, the samples passivated by AlOx:H, SiNy:H, or the stack show similar performance to samples subjected to 30 minutes of nitrogen annealing. Photoluminescence (PL) spectra corroborate our findings regarding the hydrogenation of the poly-Si layer and the c-Si substrate, with an increase in PL intensity after microwave annealing. Ultimately, our work suggests that microwave annealing could be a promising addition, offering flexibility to traditional firing hydrogenation processes.
Degradation and Accelerated Recovery of Surface Passivation in n+ Poly-Si/SiOx Passivating Contacts for TOPCon Solar Cells
We studied the surface degradation and recovery of fired poly-Si/SiOx passivating contacts during subsequent dark and illuminated annealing. We report on an industrially-viable path for accelerated recovery of surface passivation. The degradation is influenced by the type of doping in the poly-Si. Phosphorus doped n+ poly-Si/SiOx contacts show degradation followed by recovery, undoped poly-Si/SiOx contacts only show recovery during annealing. Boron doped p+ poly-Si/SiOx contacts show neither degradation nor improvement with annealing. Both degradation and recovery are thermally-activated processes and are completely reversible and cyclic in nature. The activation energy of degradation and recovery in dark for n+ poly-Si/SiOx contacts are 1.27 and 1.33 eV respectively. Dark annealing at elevated temperatures is effective for complete recovery but takes a long time (~30 min at 350 degrees C) due to higher activation energies. Annealing under 7.5 Suns of illumination lowers the activation energy for degradation and recovery to 0.88 and 0.90 eV, respectively. Using this data, we have developed an industrially viable post-firing treatment for accelerated recovery of TOPCon cells by annealing them at elevated temperatures and under intense illumination for a few minutes.
Nanopinhole-Enabled, Hole-Selective Poly-Si/SioxNy Passivating Contacts on Textured c-Si for Si Solar Cells
The next-generation silicon photovoltaics will be based on passivating electron- and hole-selective contacts with both very low interface recombination and contact resistivities. While the emerging mainstream TOPCon technology has developed excellent electron-selective poly-Si/tunneling SiOx contacts, hole-selective contacts, especially on textured surfaces, have remained a significant challenge. This contribution introduces novel high-performance hole selective poly-Si contacts on pyramid-textured Si, enabled by electrochemically produced hole transport nanopinholes in a 10 nm oxynitride passivating dielectric stack capped by p+ poly-Si. The highly passivating oxynitride layer is produced via atomic intermixing of O and N atoms in the initial SiOx/SiNy layer stack upon thermal annealing. Carrier transport is governed by nanopinhole density and size are tuned by Ag nanoparticle electrodeposition and surface attachment chemistries. This results in passivating hole contact resistivities in the m..omega..-cm2 range, while preserving interface recombination current prefactor around 5 fA/cm2.
Degradation and Accelerated Recovery of Surface Passivation in n+, p+, and Intrinsic Poly-Si/SiOx Passivating Contacts for Silicon Solar Cells
We report on the degradation and recovery of surface passivation of fired poly-Si/SiOx passivating contacts with hydrogen containing Al2O3 during annealing in the dark and under illumination. Upon firing to a peak temperature of 670 degrees C, the iVoc for symmetric test structures with n+, p+, and intrinsic poly-Si/SiOx contacts decreases due to a loss of surface passivation. Upon further annealing over the temperature range of 200-350 degrees C in the dark, depending on the type of doping, the surface passivation either shows further degradation followed by recovery, or direct recovery to the initial iVoc. Annealing at higher temperatures and/or higher illumination intensities accelerates the kinetics for both degradation and recovery processes. We show that the degradation and recovery processes are thermally activated and proceed identically in subsequent firing and annealing steps showing their cyclic nature. We present a series reaction model to explain the kinetics of degradation and recovery processes for n+ and intrinsic poly-Si/SiOx contacts. By fitting the model's rate expressions to the data, the determined effective activation energy barriers for degradation and recovery for n+ poly-Si/SiOx contacts in the dark are 1.24 and 1.51 eV, which are lowered under 7.5 Suns illumination to 0.76 and 1.15 eV, respectively.
Reliability of TOPCon Solar Cells: Understanding Degradation and Recovery of Poly-Si/SiOx Passivating Contacts
A presentation recommending that TOPCon modules and/or cells should have surface passive degradation tests performed, and should be treated with surface passivation recovery.
Passivated Contacts for Direct Wafer Product (Final Technical Report)
This TCF project developed a thin-oxide (SiO 2 )/polycrystalline silicon (poly-Si) passivated contact solar cell on CubicPV's (formally 1366 Technologies, Inc.) Direct Wafer® Product (DWP) kerfless wafers. The project used two NREL-developed technologies described in U.S. Patent No. 9,911,873, Hydrogenation of Passivated Contacts and U.S. Patent Application Serial No. 15/890,172, Doped Passivated Contacts . The project was motivated by a potential higher efficiency cell (compared to a PERC cell) using passivated contacts on the ultra-low cost kerfless wafers grown using the Direct Wafer process. The hope was to accelerate market adoption of the cell and wafer by delivering the lowest LCOE in the PV industry. The project tested both n-type and p-type SiO 2 /poly-Si passivated contacts grown by thermal oxidation and plasma enhanced chemical vapor deposition (PECVD) of the poly-Si layer on DWP with varying wafer resistivities. Both deposition techniques are industry standards and thus economically viable methods for commercializing the contacts. The results indicated that both n-type and p-type poly-Si passivated contacts can be formed on polycrystalline DWP wafers, but implied open-circuit voltages (i Voc ) were limited to below 0.65 mV (compared with ~ 730 mV on n-Cz wafers). Diffusion of H to the Si/SiO 2 /poly-Si interface was key to obtaining high i Voc values. In this study, H was diffused from a high-temperature SiN x layer deposited over the poly-Si layer during a high-temperature firing step, similar to one used for screen printed metals. The study concluded that poly-Si passivated contacts on DWP wafers passivated the surface of the wafers as well as PERC passivated surfaces, which use a less expensive dielectric layer stack. The project showed that Direct Wafer Product wafers grown by CubicPV could produce high i Voc values (~0.647 mV), which could produce a cell over 20% efficient with proper processing and metallization. These cells, though not economically viable in 2024 as a stand-alone cell, could be integrated with a wide-bandgap top solar cell to form a two-junction tandem cell that could be viable under certain circumstances. This is because the bottom cell of a 30%, two-terminal tandem only needs to be a 20% cell under one-sun conditions. Thus, the DWP could be an ideal low-cost wafer for tandems. The project also revealed that a TOPCon type cell could be formed on a p-type DWP wafer using a P-diffused emitter and a p-type poly-Si contact. In fact, the p-type version of the poly-Si contact out-performed the n-type version for a variety of wafer resistivities, from highly doped to lowly doped. This curiosity requires more work to understand because on Cz wafers, the n-type poly-Si contact is of much higher quality than the p-type version.
Development of 22.5 % p-type tunnel oxide passivated contact solar cells through efficiency enhancement by replacing local Al-BSF in PERC cells with (p+) poly-Si/SiO2 carrier selective contact
Not Available
Microwave Annealing for Fast and Effective Hydrogen Activation in Polycrystalline Silicon Passivating Contacts
Hydrogenation is a crucial step in the fabrication of high-efficiency silicon solar cells. In this study, the effectiveness of hydrogen activation is demonstrated via microwave annealing of hydrogen-rich dielectrics coated on poly-Si passivating contacts. This method is compared with conventional hydrogenation techniques, such as annealing in N2 in the presence of a hydrogen-rich source (such as hydrogenated aluminum oxide (AlOx:H), hydrogenated silicon nitride (SiNy:H), or a AlOx:H/SiNy:H stack). Key improvements observed include a reduction in J0 from 30 to <5 fA cm-2, an increase in iVoc from 690 to >730 mV, and an enhancement in effective lifetime (teff) from 0.6 to ~3.5 milliseconds on phosphorus-doped poly-Si/SiO2 passivating contact samples. With a very short annealing time of ~1-2 min, the samples passivated by AlOx:H, SiNy:H, or the stack show similar performance to samples subjected to 30 min of nitrogen annealing. Photoluminescence (PL) spectra corroborate the findings regarding the hydrogenation of the poly-Si layer and the c-Si substrate, with an increase in PL intensity after microwave annealing. Ultimately, this work suggests that microwave annealing could be a promising addition, offering flexibility to traditional firing hydrogenation processes.
Development of ~25% Efficient Double Side Screen Printed Poly-Si/SiO x Passivated Contact Solar Cells
This program aims to overcome these challenges and develop high-efficiency (24-25%) double-side (DS) TOPCon solar cells by maximizing passivation on both sides while mitigating light absorption losses. To achieve this, the program will implement either thin (≤ 20 nm) homogeneous n-TOPCon on the entire front surface or selective area thick (≥ 100 nm) n-TOPCon only underneath the front metal contact with ~90% field region composed of dielectric passivated textured n-Si in between the poly-Si/metal grid. The rear side will feature ~250 nm-thick full-area planar p-TOPCon, which functions as the rear junction. Recombination and parasitic absorption losses in the front and rear TOPCon layers will be minimized by tailoring their doping profiles and thickness. Additionally, the device performance will be further enhanced through the optimization of bulk parameters, including the carrier lifetime, resistivity, and thickness of the n-type Si absorber. Finally, advanced metallization techniques, such as fine-line printing, and floating busbar or busbar-less designs, will be employed to reduce recombination, resistive, and optical losses. The program started with the development of a technology roadmap for DS-TOPCon cells to achieve target efficiency.
Ultraviolet Laser Activation of Phosphorus-Doped Polysilicon Layers for Crystalline Silicon Solar Cells
In crystalline silicon photovoltaics (c-Si PV), a pulsed laser can be used as a substitute for a high-temperature furnace dopant diffusion/activation step. In contrast to furnace-based activation, lasers can be used to achieve highly localized doping with controlled dopant concentrations, useful in advanced architectures such as the interdigitated back contact (IBC) solar cell. In this study, a pulsed ultraviolet (UV) laser is utilized for phosphorus dopant activation within a low-pressure chemical vapor deposited (LPCVD) polycrystalline silicon (poly-Si) passivated contact layer. The highest implied open-circuit voltage iV oc values achieved using this approach reach 726 mV. However, this comes at the expense of high specific contact resistivities ρ c , which is attributed to a lower dopant concentration across the poly-Si(n + )/SiO x /c-Si interface. Regardless, the optimum iV oc , ρ c combination is measured at a laser fluence of 0.78 J cm -2 producing values of 712 mV and 89 mΩ-cm 2 , respectively. These values are still compatible with high-efficiency solar cell designs, underscoring the feasibility and effectiveness of this approach.
Self‐Assembled Monolayer Templating for Engineered Nanopinholes in Passivated Contact Solar Cells
We present a novel self-assembled monolayer (SAM)-based technique to make nanopinhole-enabled passivated contacts on silicon solar cells by tuning the SAM coverage area and etch selectivity. We deposit trimethyl-silyl Si(CH 3 ) 3 groups using hexamethyldisilazane (HMDS) as the precursor over passivating dielectric layers and their stacks (SiO 2 , SiN x , SiO 2 /SiN x ) and interrupt the HMDS attachment chemistry shortly before a full monolayer is formed on its surface. Subsequent etching in dilute HF produces pinholes through the dielectric layers due to the higher etch resistance of the SAM to HF etching. The pinhole areal density (10 4 –10 8 /cm 2 ) and size (10–1000 nm) can be tuned both by duration of HMDS attachment and HF etch time. Pinholes were characterized by atomic force microscopy, tetramethylammonium hydroxide (TMAH) selective etch, and Ag decoration by electroless plating. Polysilicon (poly-Si) passivated contacts enabled by pinholes were formed by subsequent deposition of doped amorphous silicon (a-Si:H) followed by thermal crystallization and dopant drive-in. At optimal areal pinhole density ≈10 7 /cm 2 , contacts exhibit both passivation and carrier transport via pinholes as evidenced by electron beam induced current, transmission line measurements, and carrier lifetime measurements. Solar cells based with these pinhole contacts show V oc = 723 mV and FF = 80.3%. The remaining SAM layer does not affect device performance.
Characterization of dangling bond defects at the crystalline Si/SiO x interface in a polycrystalline Si passivating contact solar cell at room temperature with electrically detected magnetic resonance spectroscopy
Monocrystalline silicon solar cells can achieve photoconversion efficiencies exceeding 26%; however, performance-limiting defects that trap carriers continue to be a challenge. In this work, we have characterized Si solar cells with tunneling SiO x /polycrystalline-Si (poly-Si) passivating contacts (TOPCon) on As-doped Czochralski Si wafers with electrically detected magnetic resonance (EDMR) spectroscopy. We fabricated 2 × 20 mm 2 TOPCon-like mini solar cells with edge passivation alongside larger 4 cm 2 sister cells and obtained similar device characteristics. We performed EDMR spectroscopy at 300 K on two minicells with different degrees of surface passivation based on the recombination parameter, J o , values of 40 and 310 fA/cm2. We optimized the resolution and the signal-to-noise ratio of the EDMR response of the minicells by varying the forward bias voltage and the magnetic field modulation amplitude. We detect two distinct signals with EDMR spectroscopy, an axial-like signal at g = 2.009, 2.0087, and 2.0015, and an isotropic signal at g = 2.0024, which we attribute to Si dangling bonds (P b0 and P b centers) and boron–oxygen related defects, respectively, at or near the c-Si/SiO x interface. The EDMR signals were lower for the cell with a lower value of J o , while the ratio of the two defect populations was very similar. The EDMR signal increases with forward bias but drops to zero at bias voltages >0.5 V, consistent with interface defects within or near the boron-doped emitter depletion region. Our study demonstrates a method to fabricate minicells that can be characterized with EDMR spectroscopy to detect industrially relevant defects in TOPCon cells.
Loss Analysis and Performance Optimization Pathways of 729-mV Voc Si Solar Cells with Poly-Si on Locally-Etched Dielectric Passivating Contacts
In this article, the loss analysis of silicon solar cells with polysilicon on locally-etched dielectric passivating contacts with Voc=729.0 mV and efficiency=22.6% has been presented. Experimentally, nano-pinholes were introduced in SiO x (2.2 nm) and SiO x /SiN y (2.2 nm/8nm) stack using metal-assisted chemical etching (MACE). SunSolve and Quokka3 were used to simulate the experimental solar cell and investigate the optical and electrical power losses. Simulations suggest maximum power loss occurs due to recombination and resistive losses in the bulk (~0.76 mW/cm2) followed by power loss due to rear contact recombination (~0.35 mW/cm2). Recombination at the front surface also contributes to 0.24 mW/cm2. The effect of improving the bulk lifetime and lowering the recombination current density at the rear side on Voc, FF and hence, efficiency has been investigated. Further, advanced structures have been proposed to minimize recombination and parasitic absorption to achieve higher Voc and Jsc of the solar cells with locally-etched dielectric passivating contacts.
Metal-Complex Inks for Lower Cost and Improved Passivation for Silicon Photovoltaic Metallization
This contribution introduces the silicon PV community to screen-printable metal-complex inks that potentially will reduce Ag usage in Si PV metallization to one-quarter and costs to one-third that of traditional particle-based pastes while also improving passivation. Metal-complex inks are formulated using a Tollen’s reaction to produce inks with a high percentage of diamminesilver (I) cations (22 wt %) in a solution of acetate and formate anions. When printed and dried, labile ammonia ligands evaporate, leaving behind silver cations which, when reduced by formate anions and acetic acid, plate out silver and silver acetate. When annealed to just 300 °C a dense metallic silver film forms with excellent conductivity, and adhesion to silicon. When compared to traditional particle-based screen-printing pastes, the metal-complex inks are much denser, have higher conductivity, use less Ag, and are a fraction of the cost. Importantly, the inks anneal from 90 – 450 °C allowing for improved passivation schemes compared with fired SiNx. This contribution highlights first experiments on the improved passivation of metallized poly-Si/SiO2 passivated contacts using metal-complex Ag inks.
Investigation of Contact Properties and Device Performance for Bifacial Double-Side Textured Silicon Solar Cells With Polysilicon Based Passivating Contacts
We investigate the impact of the surface morphology on the contact properties of phosphorus doped poly-Si layers. If the poly-Si layer on a textured surface remains intact after high-temperature metallization using a fire-through (FT) silver (Ag) paste, the J0,metal is not expected to increase significantly while the specific contact resistivity can improve with a textured surface. The contact properties of the FT Ag contacts to n+ poly-Si deposited on both textured and planar surfaces are investigated by measuring and evaluating ρc and J0,metal. The reasons for differences in contact resistance and recombination are further investigated with SEM imaging. Solar cells with n-type polysilicon based passivating contacts on the rear side are fabricated and characterized. The scientific approach used, and the insights presented in this work, help to understand the mechanisms and behavior of screen-printed and fired-through contacts to polysilicon layers deposited onto textured silicon surfaces.
Passivation Mechanisms in Locally Etched P-Type Poly-Si on Silicon Nitride/Silicon Oxide Stack
Tunneling oxide passivated contacts are quickly becoming the industry standard for high-efficiency c-Si based photovoltaic cells. Further development of these structures is essential to enable higher efficiencies and better reliability of cells. By utilizing poly-Si/SixNy/SiOx stacks, very high efficiencies have been demonstrated on small area cells. In this work we investigate the cause of the excellent passivation seen by these structures and show that the primary reason of the excellent passivation seen is the blocking B diffusion to the SiOx/c -Si interface. We also show that the interface between the silicon nitride and polysilicon affects B diffusion through to the c-Si interface. Finally, we demonstrate that the composition of the nitride used is of great importance, and that an incorrect nitride composition leads to B diffusion, and is directly correlated to poor passivation performance.
Optical Modeling of Polysilicon: TOPCon PV
Determine how film thickness changes with different deposition methods. Analyze relationship between film thickness and optical constants. The deposition rate of intrinsic polysilicon is higher during initial deposition then begins to slow down as deposition time increases. Longer depositions of polysilicon are more crystalline in structure than shorter depositions. N-type doping of polysilicon is more crystalline in structure than p-type doping, despite similar film thicknesses.