Dramatic Reduction of Silicon Surface Recombination by ALD TiOx Capping Layer from TiCl4 and H2O: The Role of Chlorine.

Amorphous thin-film TiOx prepared via atomic layer deposition (ALD) has been identified as one of the most promising materials for use in transparent passivating contacts in high-efficiency and low-cost crystalline silicon (c-Si) solar cells. As highlighted in this work, the passivation performance of ALD TiOx layers strongly depends on the metal precursor used, with films prepared using TiCl4 recently showing the best results. However, a full understanding of how such films achieve their high level of surface passivation has not yet been demonstrated. This study provides a clear demonstration that a key part of this passivation mechanism is due to chlorine (Cl) accumulation at the Si surface. This mechanism is demonstrated to be quite general in nature by showing how 2 nm of ALD TiOx (TiCl4 + H2O) can be applied as a capping layer for either ZnO or Al2O3 interlayers to dramatically reduce silicon surface recombination. Cl depth profiles obtained using secondary ion mass spectrometry confirm the presence of Cl extending through the depth of the interlayers with a peak at the silicon interface. Remarkably, this diffusion of Cl is observed following low-temperature (75 °C) deposition of the TiOx capping layer, without any subsequent thermal treatment. Contrary to earlier studies that treated residual Cl in ALD films as a general contamination issue, these findings reveal unequivocally that chlorine plays a crucial role in Si surface passivation and can be classed as an effective passivation element, similar to hydrogen in its ability to passivate Si dangling bonds. The outcomes of this research emphasize the importance of residual chlorine in enhancing the passivation of buried interfaces and provide additional motivation for employing metal chloride precursors for silicon surface passivation applications.

PO x /Al2O3 Stacks for c-Si Surface Passivation: Material and Interface Properties.

Phosphorus oxide (PO x ) capped by aluminum oxide (Al2O3) has recently been discovered to provide excellent surface passivation of crystalline silicon (c-Si). In this work, insights into the passivation mechanism of PO x /Al2O3 stacks are gained through a systematic study of the influence of deposition temperature (T dep = 100-300 °C) and annealing temperature (T ann = 200-500 °C) on the material and interface properties. It is found that employing lower deposition temperatures enables an improved passivation quality after annealing. Bulk composition, density, and optical properties vary only slightly with deposition temperature, but bonding configurations are found to be sensitive to temperature and correlated with the interface defect density (D it), which is reduced at lower deposition temperature. The fixed charge density (Q f) is in the range of + (3-9) × 1012 cm-2 and is not significantly altered by annealing, which indicates that the positively charged entities are generated during deposition. In contrast, D it decreases by 3 orders of magnitude (∼1013 to ∼1010 eV-1 cm-2) upon annealing. This excellent chemical passivation is found to be related to surface passivation provided by hydrogen, and mixing of aluminum into the PO x layer, leading to the formation of AlPO4 upon annealing.

Low-Temperature Plasma-Assisted Atomic-Layer-Deposited SnO2 as an Electron Transport Layer in Planar Perovskite Solar Cells.

In this work, we present an extensive characterization of plasma-assisted atomic-layer-deposited SnO2 layers, with the aim of identifying key material properties of SnO2 to serve as an efficient electron transport layer in perovskite solar cells (PSCs). Electrically resistive SnO2 films are fabricated at 50 °C, while a SnO2 film with a low electrical resistivity of 1.8 × 10-3 Ω cm, a carrier density of 9.6 × 1019 cm-3, and a high mobility of 36.0 cm2/V s is deposited at 200 °C. Ultraviolet photoelectron spectroscopy indicates a conduction band offset of ∼0.69 eV at the 50 °C SnO2/Cs0.05(MA0.17FA0.83)0.95Pb(I2.7Br0.3) interface. In contrast, a negligible conduction band offset is found between the 200 °C SnO2 and the perovskite. Surprisingly, comparable initial power conversion efficiencies (PCEs) of 17.5 and 17.8% are demonstrated for the champion cells using 15 nm thick SnO2 deposited at 50 and 200 °C, respectively. The latter gains in fill factor but loses in open-circuit voltage. Markedly, PSCs using the 200 °C compact SnO2 retain their initial performance at the maximum power point over 16 h under continuous one-sun illumination in inert atmosphere. Instead, the cell with the 50 °C SnO2 shows a decrease in PCE of approximately 50%.