Nonlinear Optical Susceptibilities and Linear Absorption in Phosphorene Nanoribbons: Ab initio study

TL;DR

This study uses ab initio DFT calculations to analyze the linear and nonlinear optical properties of phosphorene nanoribbons and monolayers, revealing anisotropic absorption, enhanced second-order nonlinearity, and agreement with experimental data.

Contribution

It provides the first comprehensive ab initio analysis of both linear and nonlinear optical susceptibilities in phosphorene nanoribbons, highlighting the effects of crystallographic direction and hydrogen passivation.

Findings

Optical anisotropy due to crystallographic direction.

Two orders of magnitude enhancement of second-order susceptibility in nanoribbons.

Close agreement of third-order susceptibility with experimental and semi-analytic results.

Abstract

Using Density Functional Theory (DFT) method we compute linear optical absorption spectra and nonlinear optical susceptibilities of hydrogen passivated armchair and zigzag Phosphorous Nanoribbons (aPNR and zPNR) as well as \alpha-phase phosphorous monolayer. We observe that: (a) Crystallographic direction has a strong effect on the band edge absorption which causes optical anisotropy as well as a red shift of absorption spectra by increasing the nanoribbon width. (b) The absorption values are in the order of $10^{5} cm^{-1}$ which are similar to the experimentally measured values. (c) There is two orders of magnitude enhancement of the 2nd order nonlinear optical susceptibility, $\chi^{(2)}$, in nanoribbons which emanates from breaking the centro-symmetric structure of a monolayer phosphorene by hydrogen surface terminations. (d) Chief among our results is that the 3rd order susceptibility, $\chi^{(3)}$, for phosphorene monolayer and nanoribbons are about $~10^{-13}$ esu ($~10^{-21} \frac{m^{2}}{V^{2}}$) which are in close agreement with experimentally reported values as well as a recently calculated value based on semi-analytic method. This strongly supports reliability of our method in calculating nonlinear optical susceptibilities of phosphorene and in general other nanostructures. Enhanced 2nd order optical nonlinearity in phosphorene promises better second harmonic and frequency difference (THz) generation for photonics applications.