Self-Trapped Excitons in Ionic-Covalent Silver Halide Crystals and Nanostructures: High-Frequency EPR, ESE, ENDOR and ODMR Studies

Silver halides have unique features in solid state physics because their properties are considered to be of borderline nature between ionic and covalent bonding. In AgCl, the self-trapped hole (STH) is centered and partly trapped in the cationic sublattice, forming an Ag²⁺ ion inside of a (AgCl₆)^4? complex as a result of the Jahn–Teller distortion. The STH in AgCl can capture an electron from the conduction band forming the self-trapped exciton (STE). Recent results of a study of STE by means of high-frequency electron paramagnetic resonance, electron spin echo, electron–nuclear double resonance (ENDOR) and optically detected magnetic resonance (ODMR) are reviewed. The properties of the STE in AgCl crystals, such as exchange coupling, the ordering of the triplet and singlet sublevels, the dynamical properties of the singlet and triplet states, and the hyperfine interaction with the Ag and Cl (Br) nuclei are discussed. Direct information about the spatial distribution of the wave function of STE unpaired electrons was obtained by ENDOR. From a comparison with the results of an ENDOR study of the shallow electron center and STH, it is concluded that the electron is mainly contained in a hydrogen-like 1s orbital with a Bohr radius of 15.1 ± 0.6 Å, but near its center the electron density reflects the charge distribution of the hole. The hole of the STE is virtually identical to an isolated STH center. For AgCl nanocrystals embedded into the KCl crystalline matrix, the anisotropy of the g-factor of STE and STH was found to be substantially reduced compared with that of bulk AgCl crystals, which can be explained by a considerable suppression of the Jahn–Teller effect in nanoparticles. A study of ODMR in AgBr nanocrystals in KBr revealed spatial confinement effects and allowed estimating the nanocrystal size from the shape of the ODMR spectra.