On the Issue of Textured Crystallization of Ba(NO$_3$)$_2$ in Mesoporous SiO$_2$: Raman Spectroscopy and Lattice Dynamics Analysis

TL;DR

This study investigates the lattice dynamics of Ba(NO$_3$)$_2$ nanocrystals confined in mesoporous silica using Raman spectroscopy, revealing large single-crystalline regions and insights into crystallization propagation in nanoporous media.

Contribution

It combines Raman spectroscopy, X-ray diffraction, group-theory, and ab initio calculations to analyze nanocrystal lattice dynamics and crystallization behavior in mesoporous silica.

Findings

Nanocrystals exhibit similar Raman peak positions to bulk crystals.

Large single-crystalline regions (~10-20 μm) are found within the pores.

Crystallization propagates via microporosity, contrary to initial assumptions.

Abstract

The lattice dynamics of preferentially aligned nanocrystals formed upon drying of aqueous Ba(NO$_3$)$_2$ solutions in a mesoporous silica glass traversed by tubular pores of approximately 12 nm are explored by Raman scattering. To interpret the experiments on the confined nanocrystals polarized Raman spectra of bulk single crystals and X-ray diffraction experiments are also performed. Since a cubic symmetry is inherent to Ba(NO$_3$)$_2$, a special Raman scattering geometry was utilized to separate the phonon modes of A$_g$ and E$_g$ species. Combining group-theory analysis and \textit{ab initio} lattice dynamics calculations a full interpretation of all Raman lines of the bulk single crystal is achieved. Apart from a small confinement-induced line broadening, the peak positions and normalized peak intensities of the Raman spectra of the nanoconfined and macroscopic crystals are identical. Interestingly, the Raman scattering experiment indicates the existence of comparatively large, $\sim$10-20 $\mu$m, single-crystalline regions of Ba(NO$_3$)$_2$ embedded in the porous host, near three orders of magnitude larger than the average size of single nanopores. This is contrast to the initial assumption of non-interconnected pores. It rather indicates an inter-pore propagation of the crystallization front, presumably via microporosity in the pore walls.