Jasmin Hofstetter

Precipitated iron: A limit on gettering efficacy in multicrystalline silicon

A phosphorus diffusion gettering model is used to examine the efficacy of a standard gettering process on interstitial and precipitated iron in multicrystalline silicon. The model predicts a large concentration of precipitated iron remaining after standard gettering for most as-grown iron distributions. Although changes in the precipitated iron distribution are predicted to be small, the simulated post-processing interstitial iron concentration is predicted to depend strongly on the as-grown distribution of precipitates, indicating that precipitates must be considered as internal sources of contamination during processing. To inform and validate the model, the iron distributions before and after a standard phosphorus diffusion step are studied in samples from the bottom, middle, and top of an intentionally Fe-contaminated laboratory ingot. A census of iron-silicide precipitates taken by synchrotron-based X-ray fluorescence microscopy confirms the presence of a high density of iron-silicide precipitates both before and after phosphorus diffusion. A comparable precipitated iron distribution was measured in a sister wafer after hydrogenation during a firing step. The similar distributions of precipitated iron seen after each step in the solar cell process confirm that the effect of standard gettering on precipitated iron is strongly limited as predicted by simulation. Good agreement between the experimental and simulated data supports the hypothesis that gettering kinetics is governed by not only the total iron concentration but also by the distribution of precipitated iron. Finally, future directions based on the modeling are suggested for the improvement of effective minority carrier lifetime in multicrystalline silicon solar cells.

Engineering Solutions and Root-Cause Analysis for Light-Induced Degradation in p -Type Multicrystalline Silicon PERC Modules

We identify two engineering solutions to mitigate light-induced degradation (LID) in p-type multicrystalline silicon passivated emitter and rear cells, including modification of metallization firing temperature and wafer quality. Lifetime measurements on etched-back samples confirm that LID has a strong bulk component. Spatially resolved lifetime maps indicate that the defects responsible for LID are dispersed ubiquitously across the wafer. Reversibility of LID upon low-temperature annealing suggests a low-activation-energy barrier inconsistent with precipitated impurity dissolution. Lifetime spectroscopy of the LID-affected state reveals an asymmetry of electron and hole capture cross sections of ~28.5, consistent with a deep-level donor point defect (e.g., interstitial Ti, interstitial Mo, substitutional W), charged nanoprecipitate, or charged structural defect, such as a dislocation. Finally, we explain two possible root causes of this LID, including 1) a point-defect complex involving a hydrogen atom and a deep-level donor and 2) configurational change of a point-defect complex involving fast-diffusing impurities.

Iron distribution in silicon after solar cell processing: Synchrotron analysis and predictive modeling

The evolution during silicon solar cell processing of performance-limiting iron impurities is investigated with synchrotron-based x-ray fluorescence microscopy. We find that during industrial phosphorus diffusion, bulk precipitate dissolution is incomplete in wafers with high metal content, specifically ingot border material. Postdiffusion low-temperature annealing is not found to alter appreciably the size or spatial distribution of FeSi2 precipitates, although cell efficiency improves due to a decrease in iron interstitial concentration. Gettering simulations successfully model experiment results and suggest the efficacy of high- and low-temperature processing to reduce both precipitated and interstitial iron concentrations, respectively.

Synchrotron-based analysis of chromium distributions in multicrystalline silicon for solar cells

Chromium (Cr) can degrade silicon wafer-based solar cell efficiencies at concentrations as low as 1010 cm−3. In this contribution, we employ synchrotron-based X-ray fluorescence microscopy to study chromium distributions in multicrystalline silicon in as-grown material and after phosphorous diffusion. We complement quantified precipitate size and spatial distribution with interstitial Cr concentration and minority carrier lifetime measurements to provide insight into chromium gettering kinetics and offer suggestions for minimizing the device impacts of chromium. We observe that Cr-rich precipitates in as-grown material are generally smaller than iron-rich precipitates and that Cri point defects account for only one-half of the total Cr in the as-grown material. This observation is consistent with previous hypotheses that Cr transport and CrSi2 growth are more strongly diffusion-limited during ingot cooling. We apply two phosphorous diffusion gettering profiles that both increase minority carrier lifetime ...

Lifetime Spectroscopy Investigation of Light-Induced Degradation in p-type Multicrystalline Silicon PERC

When untreated, light-induced degradation (LID) of p-type multicrystalline silicon (mc-Si)-based passivated emitter and rear cell (PERC) modules can reduce power output by up to 10% relative during sun-soaking under open-circuit conditions. Identifying the root cause of this form of LID has been the subject of several recent investigations. Lifetime spectroscopy analysis, including both injection and temperature dependencies (IDLS and TIDLS), may offer insight into the root-cause defect(s). In this paper, to illustrate the root-case defect identification method, we apply room-temperature IDLS to intentionally Cr-contaminated mc-Si. Then, we apply this technique to the p-type mc-Si that exhibits LID in PERC devices, and we provide further insights by analyzing qualitatively the injection-dependent lifetime as a function of temperature. We quantify the sensitivity of the capture cross-section ratio to variations in the measured lifetime curve and in the surface recombination. We find that the responsible defect most likely has an energy level between 0.3 and 0.7 eV above the valence band and a capture cross-section ratio between 26 and 36. Additionally, we calculate the concentrations of several candidate impurities that may cause the degradation.

High-Performance and Traditional Multicrystalline Silicon: Comparing Gettering Responses and Lifetime-Limiting Defects

In recent years, high-performance multicrystalline silicon (HPMC-Si) has emerged as an attractive alternative to traditional ingot-based multicrystalline silicon (mc-Si), with a similar cost structure but improved cell performance. Herein, we evaluate the gettering response of traditional mc-Si and HPMC-Si. Microanalytical techniques demonstrate that HPMC-Si and mc-Si share similar lifetime-limiting defect types but have different relative concentrations and distributions. HPMC-Si shows a substantial lifetime improvement after P-gettering compared with mc-Si, chiefly because of lower area fraction of dislocation-rich clusters. In both materials, the dislocation clusters and grain boundaries were associated with relatively higher interstitial iron point-defect concentrations after diffusion, which is suggestive of dissolving metal-impurity precipitates. The relatively fewer dislocation clusters in HPMC-Si are shown to exhibit similar characteristics to those found in mc-Si. Given similar governing principles, a proxy to determine relative recombination activity of dislocation clusters developed for mc-Si is successfully transferred to HPMC-Si. The lifetime in the remainder of HPMC-Si material is found to be limited by grain-boundary recombination. To reduce the recombination activity of grain boundaries in HPMC-Si, coordinated impurity control during growth, gettering, and passivation must be developed.

Study of Internal versus External Gettering of Iron during Slow Cooling Processes for Silicon Solar Cell Fabrication

The eect of slow cooling after dierent high temperature treatments on the in- terstitial iron concentration and on the electron lifetime of p-type mc-Si wafers has been in- vestigated. The respective impacts of internal relaxation gettering and external segregation gettering of metal impurities during an extended phosphorous diusion gettering are studied. It is shown that the enhanced reduction of interstitial Fe during extended P-gettering is due to an enhanced segregation gettering while faster impurities like Cu and Ni are possibly reduced due to an internal gettering eect.

Sorting Metrics for Customized Phosphorus Diffusion Gettering

Customized solar cell processing based on input material quality has the potential to increase the performance of contaminated regions of multicrystalline silicon ingots. This provides an opportunity to improve material yield and device efficiency without substantially reducing the overall throughput. Simulations and experiments show that in wafers from the top and border regions of an ingot containing as-grown iron concentrations ≳1014 cm-3, a high concentration of interstitial iron point defects, i.e., Fei, remains after standard phosphorus diffusion gettering (PDG), severely limiting electron lifetime and simulated efficiencies of PERC-type solar cells. It is shown that an extended PDG leads to a stronger reduction of Fei point defects, enabling high-efficiency devices, even on wafers from the red zone of the ingot. However, a satisfactory performance improvement after standard PDG is already achieved on wafers that contain as-grown total iron concentrations <;1014 cm-3, making the low-throughput extended PDG process unnecessary for a large fraction of the ingot. We propose using the total iron concentration and the corresponding photoluminescence contrast between grain boundaries and intragranular regions in the as-grown wafer as a simple sorting metric to determine when extended phosphorus diffusion is warranted.

Dislocation Density Reduction During Impurity Gettering in Multicrystalline Silicon

Isothermal annealing above 1250 °C has been reported to reduce the dislocation density in multicrystalline silicon (mc-Si), presumably by pairwise dislocation annihilation. However, this high-temperature process may also cause significant impurity contamination, canceling out the positive effect of dislocation density reduction on cell performance. Here, efforts are made to annihilate dislocations in mc-Si in temperatures as low as 820 °C, with the assistance of an additional driving force to stimulate dislocation motion. A reduction of more than 60% in dislocation density is observed for mc-Si containing intermediate concentrations of certain metallic species after P gettering at 820 °C. While the precise mechanism remains in discussion, available evidence suggests that the net unidirectional flux of impurities in the presence of a gettering layer may cause dislocation motion, leading to dislocation density reduction. Analysis of minority carrier lifetime as a function of dislocation density suggests that lifetime improvements after P diffusion in these samples can be attributed to the combined effects of dislocation density reduction and impurity concentration reduction. These findings suggest there may be mechanisms to reduce dislocation densities at standard solar cell processing temperatures.

Synchrotron-based investigation of transition-metal getterability in n -type multicrystalline silicon

Solar cells based on n-type multicrystalline silicon (mc-Si) wafers are a promising path to reduce the cost per kWh of photovoltaics; however, the full potential of the material and how to optimally process it are still unknown. Process optimization requires knowledge of the response of the metal-silicide precipitate distribution to processing, which has yet to be directly measured and quantified. To supply this missing piece, we use synchrotron-based micro-X-ray fluorescence (μ-XRF) to quantitatively map >250 metal-rich particles in n-type mc-Si wafers before and after phosphorus diffusion gettering (PDG). We find that 820 °C PDG is sufficient to remove precipitates of fast-diffusing impurities and that 920 °C PDG can eliminate precipitated Fe to below the detection limit of μ-XRF. Thus, the evolution of precipitated metal impurities during PDG is observed to be similar for n- and p-type mc-Si, an observation consistent with calculations of the driving forces for precipitate dissolution and segregation g...