Structural Properties of Al-O Monolayers in SiO₂ on Silicon and the Maximization of Their Negative Fixed Charge Density

Al2O3 on Si is known to form an ultrathin interfacial SiO2 during deposition and subsequent annealing, which creates a negative fixed charge (Q(fix)) that enables field-effect passivation and low surface recombination velocities in Si solar cells. Various concepts were suggested to explain the origin of this negative Q(fix). In this study, we investigate Al-O monolayers (MLs) from atomic layer deposition (ALD) sandwiched between deliberately grown/deposited SiO2 films. We show that the Al atoms have an ultralow diffusion coefficient (similar to 4 x 10(-18) cm(2)/s at 1000 degrees C), are deposited at a constant rate of similar to 5 x 10(14) Al atoms/(cm(2) cycle) from the first ALD cycle, and are tetrahedral O-coordinated because the adjacent SiO2 imprints its tetrahedral near-order and bond length into the Al-O MLs. By variation in the tunnel-SiO2 thickness and the number of Al-O MLs, we demonstrate that the tetrahedral coordination alone is not sufficient for the formation of Q(fix) but that a SiO2/Al2O3 interface within a tunneling distance from the substrate must be present. The Al-induced acceptor states at these interfaces have energy levels slightly below the Si valence band edge and require charging by electrons from either the Si substrate or from Si/SiO2 dangling bonds to create a negative Q(fix). Hence, tunneling imposes limitations for the SiO2 and Al2O3 layer thicknesses. In addition, Coulomb repulsion between the charged acceptor states results in an optimum number of Al-O MLs, i.e., separation of both interfaces. We achieve maximum negative Q(fix) of similar to 5 X 10(12) cm(-2) (comparable to thick ALD-Al2O3 on Si) with similar to 1.7 nm tunnel-SiO2 and just seven ALD-Al2O3 cycles (similar to 8 angstrom) after optimized annealing at 850 degrees C for 30 s. The findings are discussed in the context of a passivating, hole-selective tunnel contact for high-efficiency Si solar cells.