The mechanism of reversible photodegradation of 1-substituted aminoanthraquinones doped into poly(methyl methacrylate) and polystyrene is investigated. Time-dependent density functional theory is employed to predict the transition energies and corresponding oscillator strengths of the proposed reversibly-and irreversibly-damaged dye species. Ultraviolet-visible and Fourier transform infrared (FTIR) spectroscopy are used to characterize which species are present. FTIR spectroscopy indicates that both dye and polymer undergo reversible photodegradation when irradiated with a visible laser. These findings suggest that photodegradation of 1-substituted aminoanthraquinones doped in polymers originates from interactions between dyes and photoinduced thermally-degraded polymers, and the metastable product may recover or further degrade irreversibly.
INTRODUCTIONOrganic materials have a broad range of applications such as high-resolution fluorescence microscopy [1][2][3][4][5][6][7], second harmonic generation (SHG) microscopy [8][9][10][11][12], dye sensitized and polymer solar cells [13][14][15][16][17], solid state dye/organic lasers [18][19][20], and organic light emitting diodes [21,22], to name a few. Photostability of organic compounds and polymers is often a requirement for applications incorporating light-matter interaction [2-4, 6, 8, 18-20, 23-30]. When a material undergoes photodegradation, its characteristic properties deteriorate over time, which is referred to as decay; the reverse change in the characteristic properties of the material is referred to as recovery. Though photodegradation is often irreversible, the recovery process has been observed from a large variety of materials, typically involving polymers and often together with dyes, with various experimental techniques when the photodegraded materials are kept in dark for a long enough time, typically hours to days [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44].Amplified spontaneous emission (ASE) of disperse orange 11 (DO11) doped in poly(methyl methacrylate) (PMMA) bulk sample was observed to fully recover in the dark about 40 hours after photodegradation when irradiated with a 532 nm second harmonic Nd:YAG picosecond laser [33]. This self-healing phenomenon was also observed in various anthraquinone derivatives doped in PMMA and polystyrene (PS) thin films [41,42] and DO11 doped in MMA-styrene copolymers thin films [42,45] probed with transmittance image microscopy and ASE. The photodegraded thin film samples are often observed to recover partially, which suggests there exists both reversible and irreversible photodegradation. The lack of evidence for linear dichroism during photodegradation measurements eliminates orientational hole burning as the mechanism causing reversible photodegra- [38,42,46,[50][51][52][53][54], they have failed to elucidate the underlying mechanism.Several hypotheses of the mechanism responsible for reversible photodegradation in DO11/PMMA have been proposed, including intramolecular proton transfer and ...