Orange Organic Long-persistent Luminescence from an Electron Donor/Acceptor Binary System

Organic long-persistent luminescence (LPL) materials can overcome the disadvantages of inorganic LPL materials in terms of element sustainability, processability, and color tunability. However, all published electron donor/acceptor binary organic LPL systems show green emission. Here, we report an organic LPL system consisting of N,N,N\u27,N\u27-tetrakis(p-diisobutylaminophenyl)-p-phenylenediamine (TBAPD) as a donor dopant and 2,8-bis(diphenylphosphoryl)dibenzo[b,d]thiophene (PPT) as an acceptor host. The TBAPD/PPT film exhibits orange photoluminescence (CIEx, CIEy = 0.49, 0.49) and LPL (CIEx, CIEy = 0.51, 0.48)

Influence of energy gap between charge-transfer and locally excited states on organic long persistence luminescence

Organic long-persistent luminescence (LPL) is an organic luminescence system that slowly releases stored exciton energy as light. Organic LPL materials have several advantages over inorganic LPL materials in terms of functionality, flexibility, transparency, and solution-processability. However, the molecular selection strategies for the organic LPL system still remain unclear. Here we report that the energy gap between the lowest localized triplet excited state and the lowest singlet charge-transfer excited state in the exciplex system significantly controls the LPL performance. Changes in the LPL duration and spectra properties are systematically investigated for three donor materials having a different energy gap. When the energy level of the lowest localized triplet excited state is much lower than that of the charge-transfer excited state, the system exhibits a short LPL duration and clear two distinct emission features originating from exciplex fluorescence and donor phosphorescence

Many Exciplex Systems Exhibit Organic Long‐Persistent Luminescence

Organic long‐persistent luminescence (OLPL) is a long‐lasting luminescence from a photogenerated intermediated state, such as a charge separated state. Here, it is shown that many exciplex systems exhibit OLPL and that emission pathways of OLPL can be controlled by the relationship among local excited states and charge‐transfer excited states of materials

Evidence and mechanism of efficient thermally activated delayed fluorescence promoted by delocalized excited states

The design of organic compounds with nearly no gap between the first excited singlet (S1) and triplet (T1) states has been demonstrated to result in an efficient spin-flip transition from the T1 to S1 state, that is, reverse intersystem crossing (RISC), and facilitate light emission as thermally activated delayed fluorescence (TADF). However, many TADF molecules have shown that a relatively appreciable energy difference between the S1 and T1 states (~0.2 eV) could also result in a high RISC rate. We revealed from a comprehensive study of optical properties of TADF molecules that the formation of delocalized states is the key to efficient RISC and identified a chemical template for these materials. In addition, simple structural confinement further enhances RISC by suppressing structural relaxation in the triplet states. Our findings aid in designing advanced organic molecules with a high rate of RISC and, thus, achieving the maximum theoretical electroluminescence efficiency in organic light-emitting diodes

Long-lived efficient delayed fluorescence organic light-emitting diodes using n-type hosts.

Organic light-emitting diodes have become a mainstream display technology because of their desirable features. Third-generation electroluminescent devices that emit light through a mechanism called thermally activated delayed fluorescence are currently garnering much attention. However, unsatisfactory device stability is still an unresolved issue in this field. Here we demonstrate that electron-transporting n-type hosts, which typically include an acceptor moiety in their chemical structure, have the intrinsic ability to balance the charge fluxes and broaden the recombination zone in delayed fluorescence organic electroluminescent devices, while at the same time preventing the formation of high-energy excitons. The n-type hosts lengthen the lifetimes of green and blue delayed fluorescence devices by > 30 and 1000 times, respectively. Our results indicate that n-type hosts are suitable to realize stable delayed fluorescence organic electroluminescent devices

Exact solution of kinetic analysis for thermally activated delayed fluorescence materials

Research at Kyushu, Kyoto and St Andrews Universities was supported by EPSRC and JSPS Core to Core grants (JSPS Core-to-core Program; EPSRC grant number EP/R035164/1). Authors are also grateful for financial support from the Program for Building Regional Innovation Ecosystems of the Ministry of Education, Culture, Sports, Science and Technology, Japan, JST ERATO Grant JPMJER1305, JSPS KAKENHI JP20H05840, and Kyulux Inc.The photophysical analysis of thermally activated delayed fluorescence (TADF) materials has become instrumental to providing insight into their stability and performance, which is not only relevant for organic light-emitting diodes (OLED), but also for other applications such as sensing, imaging and photocatalysis. Thus, a deeper understanding of the photophysics underpinning the TADF mechanism is required to push materials design further. Previously reported analyses in the literature of the kinetics of the various processes occurring in a TADF material rely on several a priori assumptions to estimate the rate constants for forward and reverse intersystem crossing (ISC and RISC, respectively). In this report, we demonstrate a method to determine these rate constants using a three-state model together with a steady-state approximation and, importantly, no additional assumptions. Further, we derive the exact rate equations, greatly facilitating a comparison of the TADF properties of structurally diverse emitters and providing a comprehensive understanding of the photophysics of these systems.PostprintPostprintPeer reviewe

Twisting of Porphyrin by Assembly in a Metal‐Organic Framework yielding Chiral Photoconducting Films for Circularly‐Polarized‐Light Detection

While materials based on organic molecules usually have either superior optoelectronic or superior chiral properties, the combination of both is scarce. Here, a crystalline chiroptical film based on porphyrin with homochiral side groups is presented. While the dissolved molecule has a planar, thus, achiral porphyrin core, upon assembly in a metal–organic framework (MOF) film, the porphyrin core is twisted and chiral. The close packing and the crystalline order of the porphyrin cores in the MOF film also results in excellent optoelectronic properties. By exciting the Soret band of porphyrin, efficient photoconduction with a high On-Off-ratio is realized. More important, handedness-dependent circularly-polarized-light photoconduction with a dissymmetry factor g of 4.3×10$^{−4}$ is obtained. We foresee the combination of such assembly-induced chirality with the rich porphyrin chemistry will enable a plethora of organic materials with exceptional chiral and optoelectronic properties

Organic long persistent luminescence from a thermally activated delayed fluorescence compound

Funding: UK EPSRC (grants EP/ P010482/1, EP/J01771X, EP/J00916, and EP/R035164/1). We gratefully acknowledge funding through the EPSRC NSFCBET lead agency agreement (EP/R010595/1,1706207) and a Leverhulme Trust Research Grant (RPG-2017-231).Organic long‐persistent luminescence (OLPL) is one of the most promising methods for long‐lived‐emission applications. However, present room‐temperature OLPL emitters are mainly based on a bimolecular exciplex system which usually needs an expensive small molecule such as 2,8‐bis(diphenyl‐phosphoryl)dibenzo[b,d]thiophene (PPT) as the acceptor. In this study, a new thermally activated delayed fluorescence (TADF) compound, 3‐(4‐(9H‐carbazol‐9‐yl)phenyl)acenaphtho[1,2‐b]pyrazine‐8,9‐dicarbonitrile (CzPhAP), is designed, which also shows OLPL in many well‐known hosts such as PPT, 2,2′,2″‐(1,3,5‐benzinetriyl)‐tris(1‐phenyl‐1‐H‐benzimidazole) (TPBi), and poly(methyl methacrylate) (PMMA), without any exciplex formation, and its OLPL duration reaches more than 1 h at room temperature. Combining the low cost of PMMA manufacture and flexible designs of TADF molecules, pure organic, large‐scale, color tunable, and low‐cost room‐temperature OLPL applications become possible. Moreover, it is found that the onset of the 77 K afterglow spectra from a TADF‐emitter‐doped film is not necessarily reliable for determining the lowest triplet state energy level. This is because in some TADF‐emitter‐doped films, optical excitation can generate charges (electron and holes) that can later recombine to form singlet excitons during the phosphorescence spectrum measurement. The spectrum taken in the phosphorescence time window at low temperature may consequently consist of both singlet and triplet emission.Publisher PDFPeer reviewe

1,4-bis(2,2-diphenylethenyl)benzene as an efficient emitting material for organic light emitting diodes

We report on the photophysical properties of 1,4-bis(2,2-diphenylethenyl)benzene (PEB) in a solution and a solid state. A poor blue photoluminescence efficiency of PEB in a solution dramatically increases in the deposited film. We explain such properties in terms of molecular dynamics and degrees of intramolecular freedom in various molecular environments. PEB as an electron-transport and emitting layer in organic light-emitting diodes (OLEDs) shows bright blue-green electroluminescence (EL) with the peak wavelength at λmax ~ 495 nm. The maximum external EL quantum efficiency of ηEL = 2.5 % and maximum luminance of 41600 cd/m2 in the optimized device were obtained, indicating that PEB possesses superior electron-transport ability