Optical absorption of excimer laser-induced dichlorine monoxide in silica glass and excitation of singlet oxygen luminescence by energy transfer from chlorine molecules

TL;DR

This study identifies optical absorption features of dichlorine monoxide in irradiated silica glass and demonstrates energy transfer from chlorine molecules to singlet oxygen, impacting glass solarization.

Contribution

It provides the first detailed analysis of Cl2O optical absorption in silica and shows energy transfer to O2, revealing new pathways affecting glass properties.

Findings

Identification of a 4.7 eV absorption band of Cl2O in silica

Observation of singlet O2 luminescence via energy transfer from Cl2 molecules

Thermal destruction of Cl2O absorption band between 300C and 400C

Abstract

An optical absorption (OA) band of interstitial dichlorine monoxide molecules with peak at 4.7 eV and halfwidth 0.94 eV is identified in F2 laser - irradiated (photon energy=7.9 eV) synthetic silica glass bearing both interstitial O2 and Cl2 molecules. Alongside with intrinsic defects, this OA band can contribute to solarization of silica glasses produced from SiCl4. While the formation of ClClO is confirmed by its Raman signature, its structural isomer ClOCl may also contribute to this induced OA band. Thermal destruction of this band between 300C and 400C almost completely restores the pre-irradiation concentration of interstitial Cl2. An additional weak OA band at 3.5 eV is tentatively assigned to ClO2 molecules. The strongly forbidden 1272nm infrared luminescence band of excited singlet O2 molecules was observed at 3 eV-3.5 eV excitation, demonstrating an energy transfer process from photoexcited triplet Cl2 to O2. The energy transfer most likely occurs between Cl2 and O2 interstitial molecules located in neighboring nanosized interstitial voids in the structure of SiO2 glass network.