The Influence of Alkali metals Interaction with Al/P‐Substituted BN Nanosheets on Their Electronic and Nonlinear Optical Properties: A DFT Theoretical Study

Abstract

On the basis of the boron nitride (BN) nanosheet, the Al/Psubstituted and alkali-doped M@Al-BN, M'@Al-BN, M@P-BN, and M'@P-BN (M, M' = Li, Na, K) compounds were designed to study how the dopants affect the nonlinear optical (NLO) responses. The alkali metal atoms on the Al/P-substituted BN nanosheets are located inside or outside the bowl. The results show that doping the alkali metal atoms can significantly reduce the energy gaps of the undoped systems, which is mainly attributed to the new high HOMO level containing excess electrons. These doped species possess the electride characteristics and exhibit large static first hyperpolarizabilities (β 0 ) in the range of 1807-60919 au. Especially, the loosely bound excess electron from alkali metal atom brings the considerable β 0 to Na'/K'@Al-BN and M/M'@P-BN systems. In addition, the introduction of an alkali atom significantly enhances the β 0 of P-BN compared to corresponding Al-BN because these compounds have much smaller transition energies. These findings may provide valuable insights into the design of new high-performance NLO materials based on BN nanosheets.[a] Dr. ). The authors also acknowledge the National Supercomputing Center in Shenzhen for providing computational resources.

Demonstrating the Potential of Alkali Metal-Doped Cyclic C6O6Li6 Organometallics as Electrides and High-Performance NLO Materials

“…As we know, alkali metals have a low ionization energy, due to which they can easily donate electrons to the system and results in an increase of the electron number. Thus, the NLO response will be enhanced due to the increasing number of electrons. − For example, the doping of inorganic Al 12 N 12 nanocages into alkali metals narrowed the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap to a range of 0.49–0.71 eV. Furthermore, the value of hyperpolarizability (β o ) is also increased, which resulted in a large NLO response. , …”

Mixed superalkalis are a better choice than pure superalkalis for B12N12 nanocages to design high-performance nonlinear optical materials

“…The interaction and vertical ionization energies are the best tools for studying the stabilities of complexes. 66,67 Mixed superalkalis possess lower ionization potentials than those of alkali metal atoms, so higher binding energies are expected to be shown by their complexes. 53,68 To confirm the stability of complexes A-G, their interaction energies are determined and given in Table 1.…”

Exploring the second-order polarizability of copper doped silicon carbide nanocluster: toward a new NLO material

“…Hou et al, investigated the doping of alkali metal on Al/P substituted BN nanosheet for NLO response. A value of β o upto 6.09 ×10 5 au is reported for the Al/P substituted BN [38]. Solimannejad et al, probed the alkali metals doping on the Si 12 C 12 nanocage for non-linear response.…”