Metal‐free organic triplet emitters are an emerging class of organic semiconducting material. Among them, molecules with tunable emission responsive to environmental stimuli have shown great potential in solid‐state lighting, sensors, and anti‐counterfeiting systems. Here, a novel excited‐state intramolecular proton transfer (ESIPT) system is proposed showing the activation of thermally activated delayed fluorescence (TADF) or room‐temperature phosphorescence (RTP) simultaneously from both keto and enol tautomers. The prototype ESIPT triplet emitters exhibit up to 50% delayed emission quantum yield. Their enol–keto tautomerization can be switched by controlling the matrix acidity in doped polymer films. Taking advantage of these unique properties, “on‐off” switchable triplet emission systems controlled by acid vapor annealing, as well as photopatterning systems capable of generating facile and high‐contrast emissive patterns, are devised.
A new type of luminescence switching behavior based on phosphorescence enhancement from a series of metal‐free organic phosphors doped polymers by UV‐irradiation is investigated. This phenomenon is observed only from pairs of organic phosphors and polymer matrices having a combination of appropriate triplet exciton lifetime and oxygen permeability. Systematic investigation reveals that the luminescence switching behavior of organic phosphors embedded in a specific polymeric matrix stems from the conversion of triplet oxygens to singlet oxygens by UV‐irradiation, leading to the unique phosphorescence enhancement of organic phosphors. Visualization of latent information by UV‐irradiation is demonstrated toward novel secure information communication applications.
more » « less- PAR ID:
- 10455073
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Optical Materials
- Volume:
- 8
- Issue:
- 23
- ISSN:
- 2195-1071
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract -
Abstract The highly sensitive optical detection of oxygen including dissolved oxygen (DO) is of great interest in various applications. We devised a novel room‐temperature‐phosphorescence (RTP)‐based oxygen detection platform by constructing core–shell nanoparticles with water‐soluble polymethyloxazoline shells and oxygen‐permeable polystyrene cores crosslinked with metal‐free purely organic phosphors. The resulting nanoparticles show a very high sensitivity for DO with a limit of detection (LOD) of 60 n
m and can be readily used for oxygen quantification in aqueous environments as well as the gaseous phase. -
Abstract Visible-light and infrared-light persistent phosphors are extensively studied and are being used as self-sustained glowing tags in darkness. In contrast, persistent phosphors for higher-energy, solar-blind ultraviolet-C wavelengths (200–280 nm) are lacking. Also, persistent tags working in bright environments are not available. Here we report five types of Pr3+-doped silicates (melilite, cyclosilicate, silicate garnet, oxyorthosilicate, and orthosilicate) ultraviolet-C persistent phosphors that can act as self-sustained glowing tags in bright environments. These ultraviolet-C persistent phosphors can be effectively charged by a standard 254 nm lamp and emit intense, long-lasting afterglow at 265–270 nm, which can be clearly monitored and imaged by a corona camera in daylight and room light. Besides thermal-stimulation, in bright environments, photo-stimulation also contributes to the afterglow emission and its contribution can be dominant when ambient light is strong. This study expands persistent luminescence research to the ultraviolet-C wavelengths and brings persistent luminescence applications to light.
-
Abstract The optical properties of a textured antireflective coating (ARC) polymeric film are engineered by combining the down‐conversion effect of large phosphor particles and the multiple scattering effect of SiO2nanoparticles. In order to address the parasitic absorption of ultraviolet (UV) light, phosphors are added to convert UV light to visible light. However, the embedded phosphors increase the reflectance of the ARC film, due to the large particle size (>5 µm) and high refractive index (
n ≈ 1.9) of phosphors. Such a backward scattering problem of phosphors is compensated by adding spherical SiO2nanoparticles. Experimental and computational results show that SiO2nanoparticles in the ARC film decrease the reflectance by increasing the diffuse transmittance. This optically engineered ARC film successfully promotes the light absorption of the perovskite/silicon tandem solar cell, leading to the improvement of power conversion efficiency of the tandem cell from 22.48% to 23.50%. -
Solid-state photoreactions are generally controlled by the rigid and ordered nature of crystals. Herein, the solution and solid-state photoreactivities of carbonylbis(4,1-phenylene)dicarbonazidate (1) were investigated to elucidate the solid-state reaction mechanism. Irradiation of 1 in methanol yielded primarily the corresponding amine, whereas irradiation in the solid state gave a mixture of photoproducts. Laser flash photolysis in methanol showed the formation of the triplet ketone (TK) of 1 (τ ∼ 99 ns), which decayed to triplet nitrene 31N (τ ∼ 464 ns), as assigned by comparison to its calculated spectrum. Laser flash photolysis of a nanocrystalline suspension and diffuse reflectance laser flash photolysis also revealed the formation of TK of 1 (τ ∼ 106 ns) and 31N (τ ∼ 806 ns). Electron spin resonance spectroscopy and phosphorescence measurements further verified the formation of 31N and the TK of 1, respectively. In methanol, 31N decays by H atom abstraction. However, in the solid state, 31N is sufficiently long lived to thermally populate its singlet configuration (11N). Insertion of 11N into the phenyl ring to produce oxazolone competes with 31N cleavage to form a radical pair. Notably, 1 did not exhibit photodynamic behavior, likely because the photoreaction occurs only on the crystal surfaces.more » « less