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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. Keywords: Defects; dislocation recombination activity; dislocations; eccentricity variation; high-performance multicrystalline silicon (HPMC-Si); minority-carrier lifetime; photovoltaics; recombination; synchrotron, United States. Department of Energy (Contract EEC-1041895), National Science Foundation (U.S.) (Contract EEC-1041895)

The bulk minority-carrier lifetime in p-And n-type kerfless epitaxial (epi) crystalline silicon wafers is shown to increase >500× during phosphorus gettering. We employ kinetic defect simulations and microstructural characterization techniques to elucidate the root cause of this exceptional gettering response. Simulations and deep-level transient spectroscopy (DLTS) indicate that a high concentration of point defects (likely Pt) is "locked in" during fast (60 °C/min) cooling during epi wafer growth. The fine dispersion of moderately fast-diffusing recombination-active point defects limits as-grown lifetime but can also be removed during gettering, confirmed by DLTS measurements. Synchrotron-based X-ray fluorescence microscopy indicates metal agglomerates at structural defects, yet the structural defect density is sufficiently low to enable high lifetimes. Consequently, after phosphorus diffusion gettering, epi silicon exhibits a higher lifetime than materials with similar bulk impurity contents but higher densities of structural defects, including multicrystalline ingot and ribbon silicon materials. Device simulations suggest a solar-cell efficiency potential of this material >23%., United States. Department of Energy (Contract DE-EE0005314), United States. Department of Energy (Contract EEC-1041895), National Science Foundation (U.S.) (Contract EEC-1041895)

Chromium (Cr) can degrade silicon wafer-based solar cell efficiencies at concentrations as low as 10¹⁰cm⁻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 Cr[subscript i] 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 by two orders of magnitude and reduce [Cr[subscript i]] by three orders of magnitude to 10¹⁰cm⁻³. Some Cr-rich precipitates persist after both processes, and locally high [Cr[subscript i]] after the high-temperature process indicates that further optimization of the chromium gettering profile is possible., United States. Department of Energy (Contract DE-EE0005314), National Science Foundation (U.S.) (Contract EEC-1041895), United States. Department of Energy (Contract EEC-1041895), National Science Foundation (U.S.) (Grant 1122374)

We couple numerical process and device simulations to provide a framework for understanding the combined effects of as-grown wafer impurity distribution, processing parameters, and solar cell architecture. For this study, we added the Impurity-to-Efficiency simulator to Synopsys’ Sentaurus Process software using the Alagator Scripting Language. Our results quantify how advanced processing can eliminate differences in efficiency due to different as-grown impurity concentrations and due to different area fractions of defective wafer regions. We identify combinations of as-grown impurity distributions and process parameters that produce solar cells limited by point defects and those that are limited by precipitated impurities. Gettering targeted at either point defect or precipitate reduction can then be designed and applied to increase cell efficiency. We also visualize the post-processing iron and total recombination distributions in 2D maps of the wafer cross-section. PV researchers and companies can input their initial iron distributions and processing parameters into our software and couple the resulting process simulation results with a solar cell device design of interest to conduct their own analyses. The Alagator scripts we developed are freely available online at http://pv.mit.edu/impurity-to-efficiency-i2e-simulator-for-sentaurus-tcad/., National Science Foundation (U.S.) (Grant EEC-1041895), United States. Dept. of Energy (Award DE-EE0006335), American Society for Engineering Education. National Defense Science and Engineering Graduate Fellowship, Alexander von Humboldt Foundation (Feodor Lynen Research Fellowship)

Silicon wafers comprise approximately 40% of crystalline silicon module cost, and represent an area of great technological innovation potential. Paradoxically, unconventional wafer-growth techniques have thus far failed to displace multicrystalline and Czochralski silicon, despite four decades of innovation. One of the shortcomings of most unconventional materials has been a persistent carrier lifetime deficit in comparison to established wafer technologies, which limits the device efficiency potential. In this perspective article, we review a defect-management framework that has proven successful in enabling millisecond lifetimes in kerfless and cast materials. Control of dislocations and slowly diffusing metal point defects during growth, coupled to effective control of fast-diffusing species during cell processing, is critical to enable high cell efficiencies. To accelerate the pace of novel wafer development, we discuss approaches to rapidly evaluate the device efficiency potential of unconventional wafers from injection-dependent lifetime measurements.

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.

An important aspect of Process Simulators for photovoltaics is prediction of defect evolution during device fabrication. Over the last twenty years, these tools have accelerated process optimization, and several Process Simulators for iron, a ubiquitous and deleterious impurity in silicon, have been developed. The diversity of these tools can make it difficult to build intuition about the physics governing iron behavior during processing. Thus, in one unified software environment and using self-consistent terminology, we combine and describe three of these Simulators. We vary structural defect distribution and iron precipitation equations to create eight distinct Models, which we then use to simulate different stages of processing. We find that the structural defect distribution influences the final interstitial iron concentration ([Fe[subscript i]]) more strongly than the iron precipitation equations. We identify two regimes of iron behavior: (1) diffusivity-limited, in which iron evolution is kinetically limited and bulk ([Fe[subscript i]]) predictions can vary by an order of magnitude or more, and (2) solubility-limited, in which iron evolution is near thermodynamic equilibrium and the Models yield similar results. This rigorous analysis provides new intuition that can inform Process Simulation, material, and process development, and it enables scientists and engineers to choose an appropriate level of Model complexity based on wafer type and quality, processing conditions, and available computation time., National Science Foundation (U.S.), United States. Dept. of Energy (NSF CA No. EEC-1041895), Tekes (Agency) (project ‘‘PASSI’’ (project No. 2196/31/ 2011)), Academy of Finland (project ‘‘Low- Cost Photovoltaics.’’), German Federal Ministry for the Environment, Nature Conservation and Nuclear (research cluster ‘‘SolarWinS’’ (contract No. 0325270A-H)), Alexander von Humboldt-Stiftung (Feodor Lynen Postdoctoral Fellowship), Massachusetts Institute of Technology. Department of Mechanical Engineering (Peabody Visiting Professorship), Harvard University (Real Colegio Complutense, RCC Fellowship), Finnish Cultural Foundation (grant No. 00150504)

Dislocations limit solar cell performance bydecreasing minority carrier diffusion length, leading to inefficientcharge collection at the device contacts. However, studieshave shown that the recombination strength of dislocationclusters within millimeters away from each other can vary byorders of magnitude. In this contribution, we present correlations between dislocation microstructure and recombination activity levels which span close to two orders of magnitude. We discuss a general trend observed: higherdislocation recombination activity appears to be correlated witha higher degree of impurity decoration, and a higher degree ofdisorder in the spatial distribution of etch pits. We present anapproach to quantify the degree of disorder of dislocationclusters. Based on our observations, we hypothesize that therecombination activity of different dislocation clusters can bepredicted by visual inspection of the etch pit distribution andgeometry., This poster got a poster award.

Dislocation clusters in multicrystalline silicon limit solar cell performance by decreasing minoritycarrier diffusion length. Studies have shown that the recombination strength of dislocation clusterscan vary by up to two orders of magnitude, even within the same wafer. In this contribution, wecombine a surface-analysis approach with bulk characterization techniques to explore theunderlying root cause of variations in recombination strength among different clusters. We observethat dislocation clusters with higher recombination strength consist of dislocations with a largervariation of line vector, correlated with a higher degree of variation in dislocation etch-pit shapes(ellipticities). Conversely, dislocation clusters exhibiting the lowest recombination strength containmostly dislocations with identical line vectors, resulting in very similar etch-pit shapes. Thedisorder of dislocation line vector in high-recombination clusters appears to be correlated withimpurity decoration, possibly the cause of the enhanced recombination activity. Based on ourobservations, we conclude that the relative recombination activity of different dislocation clustersin the device may be predicted via an optical inspection of the distribution and shape variation ofdislocation etch pits in the as-grown wafer.

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.

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 FeSi[subscript 2] 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., United States. Dept. of Energy (Contract DE-FG36-09GO1900), Spanish Ministry of Science and Innovation (Thincells Project TEC2008-06798-C03-02)

Synchrotron-based X-ray fluorescence microscopy is applied to study the evolution of iron silicide precipitates during phosphorus diffusion gettering and low-temperature annealing. Heavily Fe-contaminated ingot border material contains FeSi2 precipitates after rapid in-line P-diffusion firing, suggesting kinetically limited gettering in these regions. An impurity-to-efficiency (I2E) gettering model is developed to explain the results. The model demonstrates the efficacy of high- and medium-temperature processing on reducing the interstitial iron population over a range of process parameters available to industry., United States. Dept. of Energy (contract number DE-FG36-09GO1900), National Science Foundation (U.S.) (NSF Graduate Research Fellowship), Barcelona Chamber of Commerce (MIT-Spain/La Cambra de Barcelona Seed Fund)

The extraction of metal impurities during phosphorus diffusion gettering (PDG) is one of the crucial process steps when fabricating high-efficiency solar cells using low-cost, lower-purity silicon wafers. In this work, we show that for a given metal concentration, the size and density of metal silicide precipitates strongly influences the gettering efficacy. Different precipitate size distributions can be already found in silicon wafers grown by different techniques. In our experiment, however, the as-grown distribution of precipitated metals in multicrystalline Si sister wafers is engineered through different annealing treatments in order to control for the concentration and distribution of other defects. A high density of small precipitates is formed during a homogenization step, and a lower density of larger precipitates is formed during extended annealing at 740º C. After PDG, homogenized samples show a decreased interstitial iron concentration compared to as-grown and ripened samples, in agreement with simulations.

The introduction of a low-temperature (LT) tail after P emitter diffusion was shown to lead to considerable improvements in electron lifetime and solar cell performance by different researchers. So far, the drawback of the investigated extended gettering treatments has been the lack of knowledge about optimum annealing times and temperatures and the important increase in processing time. In this manuscript, we calculate optimum annealing temperatures of Fe-contaminated Si wafers for different annealing durations. Subsequently, it is shown theoretically and experimentally that a relatively short LT tail of 15 min can lead to a significant reduction of interstitial Fe and an increase in electron lifetime. Finally, we calculate the potential improvement of solar cell efficiency when such a short-tail extended P diffusion gettering is included in an industrial fabrication process.

The evolution during silicon solar cell processing of performance-limiting iron impurities isinvestigated with synchrotron-based x-ray fluorescence microscopy. We find that during industrialphosphorus diffusion, bulk precipitate dissolution is incomplete in wafers with high metal content,specifically ingot border material. Postdiffusion low-temperature annealing is not found to alterappreciably the size or spatial distribution of FeSi2precipitates, although cell efficiency improvesdue to a decrease in iron interstitial concentration. Gettering simulations successfully modelexperiment results and suggest the efficacy of high- and low-temperature processing to reduce bothprecipitated and interstitial iron concentrations, respectively.

The e�ect of slow cooling after di�erent 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 di�usion 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 e�ect.