Results available in the literature on minority carrier trapping and light‐induced degradation (LID) effects in silicon materials containing boron and oxygen atoms are briefly reviewed. Special attention is paid to the phenomena associated with “deep” electron traps (J. A. Hornbeck and J. R. Haynes, Phys. Rev. 1955, 97, 311) and the recently reported results that have linked LID with the transformation of a defect consisting of a substitutional boron atom and an oxygen dimer (BsO2) from a configuration with a deep donor state into a recombination active configuration associated with a shallow acceptor state (M. Vaqueiro‐Contreras et al., J. Appl. Phys. 2019, 125, 185704). It is shown that the BsO2 complex is a defect with negative‐U properties, and it is responsible for minority carrier trapping and persistent photoconductivity in nondegraded Si:B+O samples and solar cells. It is argued that the “deep” electron traps observed by Hornbeck and Haynes are the precursors of the “slow” forming shallow acceptor defects, which are responsible for the dominant LID in boron‐doped Czochralski silicon (Cz‐Si) crystals. Both the deep and shallow defects are BsO2 complexes, transformations between charge states and atomic configurations of which account for the observed electron trapping and LID phenomena.
Float‐zone (FZ) silicon often has grown‐in defects that are thermally activated in a broad temperature window (≈300–800 °C). These defects cause efficient electron‐hole pair recombination, which deteriorates the bulk minority carrier lifetime and thereby possible photovoltaic conversion efficiencies. Little is known so far about these defects which are possibly Si‐vacancy/nitrogen‐related (VxNy). Herein, it is shown that the defect activation takes place on sub‐second timescales, as does the destruction of the defects at higher temperatures. Complete defect annihilation, however, is not achieved until nitrogen impurities are effused from the wafer, as confirmed by secondary ion mass spectrometry. Hydrogenation experiments reveal the temporary and only partial passivation of recombination centers. In combination with deep‐level transient spectroscopy, at least two possible defect states are revealed, only one of which interacts with H. With the help of density functional theory V1N1‐centers, which induce Si dangling bonds (DBs), are proposed as one possible defect candidate. Such DBs can be passivated by H. The associated formation energy, as well as their sensitivity to light‐induced free carriers, is consistent with the experimental results. These results are anticipated to contribute to a deeper understanding of bulk‐Si defects, which are pivotal for the mitigation of solar cell degradation processes.
The subject of hydrogen–boron interactions in crystalline silicon is revisited with reference to light and elevated temperature‐induced degradation (LeTID) in boron‐doped solar silicon. Ab initio modeling of structure, binding energy, and electronic properties of complexes incorporating a substitutional boron and one or two hydrogen atoms is performed. From the calculations, it is confirmed that a BH pair is electrically inert. It is found that boron can bind two H atoms. The resulting BH2 complex is a donor with a transition level estimated at E c–0.24 eV. Experimentally, the electrically active defects in n‐type Czochralski‐grown Si crystals co‐doped with phosphorus and boron, into which hydrogen is introduced by different methods, are investigated using junction capacitance techniques. In the deep‐level transient spectroscopy (DLTS) spectra of hydrogenated Si:P + B crystals subjected to heat‐treatments at 100 °C under reverse bias, an electron emission signal with an activation energy of ≈0.175 eV is detected. The trap is a donor with electronic properties close to those predicted for boron–dihydrogen. The donor character of BH2 suggests that it can be a very efficient recombination center of minority carriers in B‐doped p‐type Si crystals. A sequence of boron–hydrogen reactions, which can be related to the LeTID effect in Si:B is proposed.
Float-zone silicon has been long assumed to be bulk defect free and stable. Nevertheless, recently it was found that upon annealing between 450 °C to 700 °C detrimental defects can be activated in this material. Previous studies via deep level transient spectroscopy have identified several defect levels. However, it is still not clear which of these levels have a substantial impact on the minority carrier lifetime. In this study, we determine the recombination parameters of the dominant defect level using a combination of deep level transient spectroscopy and temperature and injection dependent lifetime spectroscopy. Additionally, we investigated the effect of hydrogenation on the thermally activated defects in ntype float-zone silicon.
Indium‐doped silicon is considered a possible p‐type material for solar cells to avoid light‐induced degradation (LID), which occurs in cells made from boron‐doped Czochralski (Cz) silicon. Herein, the defect reactions associated with indium‐related LID are examined and a deep donor is detected, which is attributed to a negative‐U defect believed to be InsO2. In the presence of minority carriers or above bandgap light, the deep donor transforms to a shallow acceptor. An analogous transformation in boron‐doped material is related to the BsO2 defect that is a precursor of the center responsible for BO LID. The electronic properties of InsO2 are determined and compared to those of the BsO2 defect. Structures of the BsO2 and InsO2 defects in different charges states are found using first‐principles modeling. The results of the modeling can explain both the similarities and the differences between the BsO2 and InsO2 properties.
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Boron-doped Czochralski grown silicon wafers dominate the photovoltaic market. Light-induced degradation of these wafers is one of the most significant roadblocks for high-efficiency solar cells. Despite a very large number of publications on this topic, only a few studies have directly investigated the precursor of the defect responsible for this degradation. In this study, using the photoconductance decay measurement method, we identify the precursor of the defect responsible for light-induced degradation. By comparing the photoconductance decay of samples in the different states, we observe the presence of a minority carrier trap in the annealed state which is not present after degradation. Trap annihilation shows a clear anticorrelation with the generation of the recombination active boron-oxygen defect, as determined from minority carrier lifetime measurements. Furthermore, it is concluded that a model based on a single-level trap cannot explain the doping-dependent measurements, meaning that the detected trap has two or more energy levels.
In this study, passivation of thermally-activated recombination centers with hydrogen in n-type float zone (FZ) Si containing nitrogen has been investigated. Prior to hydrogenation samples were heated to 550 °C using rapid thermal annealing and conventional furnaces. A large decrease in minority carrier lifetime occurred upon the heat-treatments confirming previous reports. A sequence of electron traps created in this process have been detected in the deep level transient spectra and characterized. Significant changes in the spectra have occurred after treatments in remote hydrogen plasma and subsequent annealing of the hydrogenated samples in the temperature range 100 °C–400 °C. A total elimination of electrical activity of the thermally induced defects has been observed in the hydrogenated samples subjected to annealing in the temperature range 150 °C–300 °C. The results obtained suggest a simple way for an effective cure of the degraded FZ-Si-based solar cells. Possible defect reactions occurring in the FZ-Si crystals and the role of nitrogen and carbon upon the performed treatments are discussed.
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