Ville Vähänissi

Phosphorus and boron diffusion gettering of iron in monocrystalline silicon

We have studied experimentally the phosphorus diffusion gettering (PDG) of iron in monocrystalline silicon at the temperature range of 650–800 °C. Our results fill the lack of data at low temperatures so that we can obtain a reliable segregation coefficient for iron between a phosphorus diffused layer and bulk silicon. The improved segregation coefficient is verified by time dependent PDG simulations. Comparison of the PDG to boron diffusion gettering (BDG) in the same temperature range shows PDG to be only slightly more effective than BDG. In general, we found that BDG requires more carefully designed processing conditions than PDG to reach a high gettering efficiency.

Gettering of Iron in Silicon Solar Cells With Implanted Emitters

We present here experimental results on the gettering of iron in Czochralski-grown silicon by phosphorus implantation. The gettering efficiency and the gettering mechanisms in a high resistivity implanted emitter are determined as a function of both initial iron level and gettering anneal. The results show that gettering in implanted emitters can be efficient if precipitation at the emitter is activated. This requires low gettering temperatures and/or high initial contamination level. The fastest method to getter iron from the bulk is to rapidly nucleate iron precipitates before the gettering anneal. Here, this was achieved by a fast ramp to the room temperature in between the implantation anneal and the gettering anneal.

Main defect reactions behind phosphorus diffusion gettering of iron

Phosphorus diffusion is well known to getter effectively metal impurities during silicon solar cell processing. However, the main mechanisms behind phosphorus diffusion gettering are still unclear. Here, we analyze the impact of oxygen, phosphosilicate glass as well as active and clustered phosphorus on the gettering efficiency of iron. The results indicate that two different mechanisms dominate the gettering process. First, segregation of iron through active phosphorus seems to correlate well with the gettered iron profile. Secondly, immobile oxygen appears to act as an effective gettering sink for iron further enhancing the segregation effect. Based on these findings, we present a unifying gettering model that can be used to predict the measured iron concentrations in the bulk and in the heavily phosphorus doped layers and explains the previous discrepancies reported in the literature.

Impact of Iron Precipitation on Phosphorus-Implanted Silicon Solar Cells

Ion implantation is a promising method to implement a high-performance emitter for crystalline silicon solar cells. However, an implanted emitter redistributes and mitigates harmful metal impurities to a different degree than a diffused one. This paper quantitatively assesses the effect of iron contamination level on the bulk diffusion length and open-circuit voltage of phosphorus-implanted solar cells manufactured with varying gettering parameters. By synchrotron-based micro-X-ray fluorescence measurements, we directly observe a process-dependent iron precipitate size distribution in the implanted emitters. We show that controlling the iron precipitate size distribution is important when optimizing final cell performance and discover a tradeoff between large shunting precipitates in the emitter and a high density of recombination active small precipitates in the wafer bulk. We present a heterogeneous iron precipitation model capable of reproducing the experimentally measured size distributions. We use the model to show that the dominant gettering mechanism in our samples is precipitation and that implanted emitters with surface phosphorus concentrations around 2×1019 cm-3 induce little-to-no segregation-based gettering. Based on this finding, we discuss optimal gettering strategies for industrial silicon solar cells with implanted emitters.

Black silicon significantly enhances phosphorus diffusion gettering

Black silicon (b-Si) is currently being adopted by several fields of technology, and its potential has already been demonstrated in various applications. We show here that the increased surface area of b-Si, which has generally been considered as a drawback e.g. in applications that require efficient surface passivation, can be used as an advantage: it enhances gettering of deleterious metal impurities. We demonstrate experimentally that interstitial iron concentration in intentionally contaminated silicon wafers reduces from 1.7 × 1013 cm−3 to less than 1010 cm−3 via b-Si gettering coupled with phosphorus diffusion from a POCl3 source. Simultaneously, the minority carrier lifetime increases from less than 2 μs of a contaminated wafer to more than 1.5 ms. A series of different low temperature anneals suggests segregation into the phosphorus-doped layer to be the main gettering mechanism, a notion which paves the way of adopting these results into predictive process simulators. This conclusion is supported by simulations which show that the b-Si needles are entirely heavily-doped with phosphorus after a typical POCl3 diffusion process, promoting iron segregation. Potential benefits of enhanced gettering by b-Si include the possibility to use lower quality silicon in high-efficiency photovoltaic devices.

Cu gettering by phosphorus-doped emitters in p-type silicon: Effect on light-induced degradation

The presence of copper (Cu) contamination is known to cause relevant light-induced degradation (Cu-LID) effects in p-type silicon. Due to its high diffusivity, Cu is generally regarded as a relatively benign impurity, which can be readily relocated during device fabrication from the wafer bulk, i.e. the region affected by Cu-LID, to the surface phosphorus-doped emitter. This contribution examines in detail the impact of gettering by industrially relevant phosphorus layers on the strength of Cu-LID effects. We find that phosphorus gettering does not always prevent the occurrence of Cu-LID. Specifically, air-cooling after an isothermal anneal at 800°C results in only weak impurity segregation to the phosphorus-doped layer, which turns out to be insufficient for effectively mitigating Cu-LID effects. Furthermore, we show that the gettering efficiency can be enhanced through the addition of a slow cooling ramp (-4°C/min) between 800°C and 600°C, resulting in the nearly complete disappearance of Cu-LID effects.

Iron precipitation upon gettering in phosphorus-implanted Czochralski silicon and its impact on solar cell performance

Phosphorus implantation can provide a direct route to a high-performing emitter, with no surface dead layer and improved blue response, and potentially higher open-circuit voltage. Here, iron precipitation during gettering is investigated in phosphorus-implanted, low-oxygen monocrystalline silicon and its impact on device performance evaluated. Previously, it has been shown that higher levels of initial iron contamination lead to lower final interstitial iron concentration after gettering with ion-implanted emitters, resulting in longer final bulk diffusion lengths in the more-highly contaminated materials. In this contribution, we show that despite longer bulk diffusion lengths, the open circuit-voltage of devices made from the highly iron-contaminated material can be strongly reduced. Using synchrotron-based Xray fluorescence we reveal the presence of micron-sized iron precipitates in the near surface region. While not measured over wafer-sized areas, the density of these precipitates correlates with the annealing profile. Slow-cooling from the activation anneal and proceeding directly to a 620-750°C gettering anneal results in large precipitates that are indicated as the underlying cause for the disastrous open-circuit voltage. On the other hand, quickly cooling to room temperature and then re-inserting the wafers for gettering results in very small precipitates that do not appear to have significant detrimental affects on open-circuit voltage. It is thus critical to consider the precipitation behavior of iron during gettering of ion-implanted emitters - even in monocrystalline silicon - and during low-temperature annealing in general.

Elucidation of Iron Gettering Mechanisms in Boron-Implanted Silicon Solar Cells

To facilitate cost-effective manufacturing of boron-implanted silicon solar cells as an alternative to BBr3 diffusion, we performed a quantitative test of the gettering induced by solar-typical boron-implants with the potential for low saturation current density emitters (<50 fA/cm2). We show that depending on the contamination level and the gettering anneal chosen, such boron-implanted emitters can induce more than a 99.9% reduction in bulk iron point defect concentration. The iron point defect results as well as synchrotron-based nano-X-ray-fluorescence investigations of iron precipitates formed in the implanted layer imply that, with the chosen experimental parameters, iron precipitation is the dominant gettering mechanism, with segregation-based gettering playing a smaller role. We reproduce the measured iron point defect and precipitate distributions via kinetics modeling. First, we simulate the structural defect distribution created by the implantation process, and then we model these structural defects as heterogeneous precipitation sites for iron. Unlike previous theoretical work on gettering via boron- or phosphorus-implantation, our model is free of adjustable simulation parameters. The close agreement between the model and experimental results indicates that the model successfully captures the necessary physics to describe the iron gettering mechanisms operating in boron-implanted silicon. This modeling capability allows high-performance, cost-effective implanted silicon solar cells to be designed.

Rapid thermal anneal activates light induced degradation due to copper redistribution

While it is well known that copper impurities can be relatively easily gettered from the silicon bulk to the phosphorus or boron–doped surface layers, it has remained unclear how thermally stable the gettering actually is. In this work, we show experimentally that a typical rapid thermal anneal (RTA, a few seconds at 800 °C) used commonly in the semiconductor and photovoltaic industries is sufficient to release a significant amount of Cu species from the phosphorus-doped layer to the wafer bulk. This is enough to activate the so-called copper-related light-induced degradation (Cu-LID) which results in significant minority carrier lifetime degradation. We also show that the occurrence of Cu-LID in the wafer bulk can be eliminated both by reducing the RTA peak temperature from 800 °C to 550 °C and by slowing the following cooling rate from 40–60 °C/s to 4 °C/min. The behavior is similar to what is reported for Light and Elevated Temperature degradation, indicating that the role of Cu cannot be ignored when studying other LID phenomena. Numeric simulations describing the phosphorus diffusion and the gettering process reproduce the experimental trends and elucidate the underlying physical mechanisms.While it is well known that copper impurities can be relatively easily gettered from the silicon bulk to the phosphorus or boron–doped surface layers, it has remained unclear how thermally stable the gettering actually is. In this work, we show experimentally that a typical rapid thermal anneal (RTA, a few seconds at 800 °C) used commonly in the semiconductor and photovoltaic industries is sufficient to release a significant amount of Cu species from the phosphorus-doped layer to the wafer bulk. This is enough to activate the so-called copper-related light-induced degradation (Cu-LID) which results in significant minority carrier lifetime degradation. We also show that the occurrence of Cu-LID in the wafer bulk can be eliminated both by reducing the RTA peak temperature from 800 °C to 550 °C and by slowing the following cooling rate from 40–60 °C/s to 4 °C/min. The behavior is similar to what is reported for Light and Elevated Temperature degradation, indicating that the role of Cu cannot be ignored when ...

Black silicon n-type photodiodes with high response over wide spectral range

Commercial photodiodes suffer from reflection losses and different recombination losses that reduce the collection efficiency of photogenerated charge carriers. Recently, we realized a near-ideal silicon photodiode, which steps closer to the physical performance limits of silicon photodiodes than any other silicon photodiode realized before. Our device exhibits an external quantum efficiency above 95% over the wavelength range of 235 – 980 nm, and provides a very high response at incident angles of up to 70 degrees. The high quantum efficiency is reached by 1) virtually eliminating front surface reflectance by forming a “black silicon” nanostructured surface having dimensions in the range of wavelength of optical light and 2) using an induced junction for signal collection, formed by negatively charged alumina, instead of a conventional doped p-n junction. Here, we describe the latest efforts in further development of the photodiode technology. In particular, we report improvements both in the short wavelength response via better control of the surface quality, and superior response to photons with energies close to the silicon bandgap.