Over- and Undercoordinated Atoms as a Source of Electron and Hole Traps in Amorphous Silicon Nitride (a-Si3N4).

Silicon nitride films are widely used as the charge storage layer of charge trap flash (CTF) devices due to their high charge trap densities. The nature of the charge trapping sites in these materials responsible for the memory effect in CTF devices is still unclear. Most prominently, the Si dangling bond or K-center has been identified as an amphoteric trap center. Nevertheless, experiments have shown that these dangling bonds only make up a small portion of the total density of electrical active defects, motivating the search for other charge trapping sites. Here, we use a machine-learned force field to create model structures of amorphous Si3N4 by simulating a melt-and-quench procedure with a molecular dynamics algorithm. Subsequently, we employ density functional theory in conjunction with a hybrid functional to investigate the structural properties and electronic states of our model structures. We show that electrons and holes can localize near over- and under-coordinated atoms, thereby introducing defect states in the band gap after structural relaxation. We analyze these trapping sites within a nonradiative multi-phonon model by calculating relaxation energies and thermodynamic charge transition levels. The resulting defect parameters are used to model the potential energy curves of the defect systems in different charge states and to extract the classical energy barrier for charge transfer. The high energy barriers for charge emission compared to the vanishing barriers for charge capture at the defect sites show that intrinsic electron traps can contribute to the memory effect in charge trap flash devices.

High-Accuracy Neural Network Interatomic Potential for Silicon Nitride.

In the field of machine learning (ML) and data science, it is meaningful to use the advantages of ML to create reliable interatomic potentials. Deep potential molecular dynamics (DEEPMD) are one of the most useful methods to create interatomic potentials. Among ceramic materials, amorphous silicon nitride (SiNx) features good electrical insulation, abrasion resistance, and mechanical strength, which is widely applied in industries. In our work, a neural network potential (NNP) for SiNx was created based on DEEPMD, and the NNP is confirmed to be applicable to the SiNx model. The tensile tests were simulated to compare the mechanical properties of SiNx with different compositions based on the molecular dynamic method coupled with NNP. Among these SiNx, Si3N4 has the largest elastic modulus (E) and yield stress (σs), showing the desired mechanical strength owing to the largest coordination numbers (CN) and radial distribution function (RDF). The RDFs and CNs decrease with the increase of x; meanwhile, E and σs of SiNx decrease when the proportion of Si increases. It can be concluded that the ratio of nitrogen to silicon can reflect the RDFs and CNs in micro level and macro mechanical properties of SiNx to a large extent.

Mechanistic Investigation of the Formation of Nickel Nanocrystallites Embedded in Amorphous Silicon Nitride Nanocomposites.

Herein, we report the mechanistic investigation of the formation of nickel (Ni) nanocrystallites during the formation of amorphous silicon nitride at a temperature as low as 400 °C, using perhydropolysilazane (PHPS) as a preformed precursor and further coordinated by nickel chloride (NiCl2); thus, forming the non-noble transition metal (TM) as a potential catalyst and the support in an one-step process. It was demonstrated that NiCl2 catalyzed dehydrocoupling reactions between Si-H and N-H bonds in PHPS to afford ternary silylamino groups, which resulted in the formation of a nanocomposite precursor via complex formation: Ni(II) cation of NiCl2 coordinated the ternary silylamino ligands formed in situ. By monitoring intrinsic chemical reactions during the precursor pyrolysis under inert gas atmosphere, it was revealed that the Ni-N bond formed by a nucleophilic attack of the N atom on the Ni(II) cation center, followed by Ni nucleation below 300 °C, which was promoted by the decomposition of Ni nitride species. The latter was facilitated under the hydrogen-containing atmosphere generated by the NiCl2-catalyzed dehydrocoupling reaction. The increase of the temperature to 400 °C led to the formation of a covalently-bonded amorphous Si3N4 matrix surrounding Ni nanocrystallites.