Radiative Rate Research Articles

Enhanced Intersystem Crossing, Yet Still Fluorescence Upon Introduction of Intermediate Charge-Transfer States in Hemicaged [Zn(bpy)3]2.

Photoactive zinc(II) complexes typically undergo fluorescence from the singlet excited state as the dominant radiative pathway, as the operative spin-orbit coupling is usually very small and phosphorescence from the triplet state is strongly forbidden. Although dicationic zinc(II) tris(bipyridine) strictly follows this scheme with fluorescence at λem = 326 nm, constructing the ligand sphere as a hemicage was reported to lead to quantitative intersystem crossing (ISC) and subsequent fast phosphorescence with λem = 485 and a short radiative lifetime of ca. 1 μs. Surprised by this finding, we reinvestigated [Zn(bpy)3]2+ and its hemicage derivative in great detail, including variable temperature and time-resolved photophysical measurements in solution and solid state as well as high-level theoretical calculations to resolve their excited state behavior. Our investigations suggest that both compounds undergo fluorescence at room temperature with significantly different radiative rate constants of kr = 2 × 108 and 1.2 × 106 s-1, respectively, and only weak phosphorescence on the millisecond time scale at low temperatures. The major difference is the occurrence of additional charge-transfer states within the ligand scaffold of the hemicage, which accelerate the ISC to the 3LC(bpy) state from 350 s down to 82 ns and reduce the fluorescence rate constant.

Continuous tuning of optical transition properties and phonon spectrum in Er3+ doped germano-tellurite glass system

With the development of science and the progress of technology, novel and advanced rare earth ions doped luminescent materials with higher performance are demanded in the both emerging and traditional applications. Understanding the rules for tuning the spectroscopic properties of these materials is crucial for their development. However, achieving precise control over the optical properties of rare earth doped materials using traditional design and synthesis methods, such as altering dopants and their concentrations or modifying the preparative conditions, still remains challenging. This work aims to adjust the optical transition characteristics of Er3+ doped germano-tellurite glasses by changing the glass components. First, the Er3+ doped germano-tellurite glass series were synthesized using a high-temperature melt-quenching method at optimized melting temperatures. The tuning of band gap energy and refractive index of the glasses were revealed, and it was found that both of them can be monotonically and continuously tuned by changing the glass composition. The optical transition intensity parameters of Er3+ in the glasses were calculated in the framework of traditional three-parameterized Judd-Ofelt theory using the absorption spectra, and furthermore the corresponding optical transition parameters including radiative transition rates and intrinsic lifetimes for some interested levels were alsoconfirmed. The results demonstrated that the optical transition parameters could be efficiently modulated by changing the glass composition, indicating that the spectral properties of Er3+ doped germano-tellurite glasses can be tuned for the practical applications. The reliability of the deduced tuning rule was validated by comparing the theoretical and experimental transition rate ratios of 2H11/2 → 4I15/2 to 4S3/2 → 4I15/2. Furthermore, the tuning regulation of the phonon spectra in relation to the glass composition was discovered, showing a concordance between theoretical predictions and experimental results. From the above facts, it can be concluded that the optical transition properties of Er3+ in germano-tellurite glasses can be substantially adjusted by modifying the glass composition. This work provides a new perspective for designing and developing novel luminescent materials to meet specific application needs.

Hydrodynamic simulations of cool stellar atmospheres with MANCHA

Three-dimensional time-dependent simulations of stellar atmospheres are essential to study the surface of stars other than the Sun. These simulations require the opacity binning method to reduce the computational cost of solving the radiative transfer equation down to viable limits. The method depends on a series of free parameters, among which the location and number of bins are key to set the accuracy of the resulting opacity. Our aim is to test how different binning strategies previously studied in one-dimensional models perform in three-dimensional radiative hydrodynamic simulations of stellar atmospheres. Realistic box-in-a-star simulations of the near-surface convection and photosphere of three spectral types (G2V, K0V, and M2V) were run with the MANCHA $-bins. These rates were compared with the ones computed with opacity distribution functions. Then, stellar simulations were run with grey, four-bin, and 18-bin opacities to see the impact of the opacity setup on the mean stratification of the temperature and its gradient after time evolution. The simulations of main sequence cool stars with the MANCHA code are consistent with those in the literature. For the three stars, the radiative energy exchange rates computed with 18 bins are remarkably close to the ones computed with the opacity distribution functions. The rates computed with four bins are similar to the rates computed with 18 bins, and present a significant improvement with respect to the rates computed with the Rosseland opacity, especially above the stellar surface. The Rosseland mean can reproduce the proper rates in sub-surface layers, but produces large errors for the atmospheric layers of the G2V and K0V stars. In the case of the M2V star, the Rosseland mean fails even in sub-surface layers, owing to the importance of the contribution from molecular lines in the opacity, underestimated by the harmonic mean. Similar conclusions are reached studying the mean stratification of the temperature and its gradient after time evolution.

Structural and optical characterizations of cubic GaN layers grown by MOVPE on GaAs(114) substrate

GaN-based structures have been employed in a range of electronic and optoelectronic applications. Despite the extensive utilization of hexagonal GaN (h-GaN), certain devices, such as green-emitting lasers, face limitations. Conversely, cubic GaN (c-GaN) proves advantageous in addressing challenges associated with h-GaN, thanks to its reduced bandgap and being free of the strong polarization fields resulting in enhanced radiative recombination rate. Yet, c-GaN possesses a metastable phase during growth, which can negatively impact the structure of the films. Optimizing the growth conditions can significantly improve material quality and, hence, device performance. In our present work, we report the growth of cubic GaN on GaAs (114) substrates using metal-organic vapor phase epitaxy (MOVPE) with various thicknesses. Morphological analyses demonstrated a grain structure with increased surface roughness versus layer thickness. Such measurements enabled us to study the texture and growth mode evolutions. High-resolution X-ray diffraction 2 θ-ω scans showed a (002) c-GaN preferred orientation with hexagonal inclusions. The optical characteristics of the investigated layers were explored using cathodoluminescence measurements, revealing a correlation between the stress state and layer thickness.

Impact of Crystal Orientation on Modulation Bandwidth: Towards GaN LED-Based High-Speed Visible Light Communication

Light-emitting diodes (LEDs) with high modulation bandwidth are required for high-speed visible light communication applications. Crystal orientation in the GaN LED structure plays a key factor in its modulation bandwidth as the recombination lifetime is highly dependent on crystal orientation owing to the Quantum-Confined Stark Effect (QCSE). In this study, six different crystal orientation multi-quantum well (MQW) GaN LEDs are simulated to understand the impact of heterostructure orientation on modulation bandwidth, radiative recombination rates, and emission intensity. The results of this study demonstrate that semi-polar 101¯3¯ MQW LEDs provide the highest bandwidth in the current density range of 9–20 kA/cm2 compared to the other five orientations. For instance, the semi-polar 101¯3¯-based LED offers a modulation bandwidth of 912.7 MHz at 20 kA/cm2 current density. These results suggest that the semi-polar 101¯3¯ orientation-based LED has the potential to support a high-speed visible light communication system.

Resonator embedded photonic crystal surface emitting lasers

The finite size of 2D photonic crystals results in them being a lossy resonator, with the normally emitting modes of conventional photonic crystal surface emitting lasers (PCSELs) differing in photon lifetime via their different radiative rates, and the different in-plane losses of higher order spatial modes. As a consequence, the fundamental spatial mode (lowest in-plane loss) with lowest out-of-plane scattering is the primary lasing mode. For electrically driven PCSELs, as current is increased, incomplete gain clamping results in additional spatial (and spectral) modes leading to a reduction in beam quality. A number of approaches have been discussed to enhance the area (power) scalability of epitaxy regrown PCSELs through careful design of the photonic crystal atom1–3. None of these approaches tackle the inflexibility in being unable to independently modify the photon lifetime of the different modes at the Γ2 point. As a method to introduce design flexibility, resonator embedded photonic crystal surface emitting lasers (REPCSELs) are introduced. This device, combining comparatively low coupling strength photonic crystal structures along with perimeter mirrors, allow a Fabry–Pérot resonance effect to be realised that provides wavelength selective modification of the photon lifetime. We show that surface emission of different surface emitting modes may be selectively enhanced, effectively changing the character of the modes at the Γ2 point. This is a consequence of the selective modification of in-plane loss for particular modes, and is dependent upon the alignment of the photonic crystal (PhC) band-structure and distributed Bragg reflectors’ (DBRs) reflectance spectrum. These findings offer new avenues in surface emitting laser diode engineering. The use of DBRs to reduce the lateral size of a PCSEL opens the route to small, low threshold current (Ith), high output efficiency epitaxy regrown PCSELs for high-speed communication and power sensitive sensing applications.

Advantages of AlGaN Tunnel Junction in N-Polar 284 nm Ultraviolet-B Light Emitting Diode

Smart, low cost and environmentally safe aluminum gallium nitride (AlGaN)-based ultraviolet-B light-emitting diodes (UV-B LEDs) are promising in real-world applications including medical as well as agricultural sciences. Higher efficiency droops, low hole injection efficiency, and high operating voltage are the key problems that AlGaN-based UV-B LEDs are facing. In this work, a smart and clean AlGaN-based UV-B LED at 284 nm emission wavelength has been studied. Here an approach is presented to electrically operate the quantum tunnelling probability by exploiting the transported carriers at the interface of p-AlGaN/n-AlGaN/n++-AlGaN tunnel junction (TJ) with moderate Si and Mg-doping levels and optimized thickness with the help of simulation study. The simulation results show that the Augur recombination rate is successfully suppressed and quite a high radiative recombination rate is achieved in the 284 nm N-polar AlGaN-based TJ UV-B LEDs, which is attributed to the improved hole injection toward the MQWs when compared to C-LED (conventional-LED). It is found that C-LED has a maximum IQE (internal quantum efficiency) of 40% under 200 A cm−2 injection current with an efficiency drop of 15%, while the TJ-LED has a maximum IQE of 93% with an efficiency droop of 0%. In addition, TJ-based AlGaN LED emitted power has been improved by 6 times compared to the C-LED structure. The emitted powers of TJ-LED increase linearly under varying current densities, whereas in the case of C-LED, the emitted power changes nonlinearly under varying current densities. This is attributed to the lower Augur recombination rate in the MQWs of N-AlGaN-based TJ UV-B LED. The operating voltages were reduced from 5.2 V to 4.1 V under 200 mA operation, which is attributed to the thickness and doping optimization in TJ and better selection of relatively lower Al-content in the contact layer. N-polar AlGaN-based TJ is explored for UV-B LEDs and the demonstrated work opens the door to epitaxial growth of high-performance UV emitters in MOCVD and MBE for a plethora of biomedical applications.

Quantitative prediction of rate constants and its application to organic emitters

Many phenomena in nature consist of multiple elementary processes. If we can predict all the rate constants of respective processes quantitatively, we can comprehensively predict and understand various phenomena. Here, we report that it is possible to quantitatively predict all related rate constants and quantum yields without conducting experiments, using multiple-resonance thermally activated delayed fluorescence (MR–TADF) as an example. MR–TADFs are excellent emitters because of its narrow emission, high luminescence efficiency, and chemical stability, but they have one drawback: slow reverse intersystem crossing (RISC), leading to efficiency roll-off and reduced device lifetime. Here, we show a quantum chemical calculation method for quantitatively obtaining all the rate constants and quantum yields. This study reveals a strategy to improve RISC without compromising other important factors: radiative decay rate constants, photoluminescence quantum yields, and emission linewidths. Our method can be applied in a wide range of research fields, providing comprehensive understanding of the mechanism including the time evolution of excitons.

Critical Role of Vertical Radiative Cooling Contrast in Triggering Episodic Deluges in Small‐Domain Hothouse Climates

AbstractSeeley and Wordsworth (2021, https://doi.org/10.1038/s41586‐021‐03919‐z) showed that in small‐domain cloud‐resolving simulations the temporal pattern of precipitation transforms in extremely hot climates (≥320 K) from quasi‐steady to organized episodic deluges, with outbursts of heavy rain alternating with several dry days. They proposed a mechanism for this transition involving increased water vapor greenhouse effect and solar radiation absorption leading to net lower‐tropospheric radiative heating. This heating inhibits lower‐tropospheric convection and decouples the boundary layer from the upper troposphere during the dry phase, allowing lower‐tropospheric moist static energy to build until it discharges, resulting in a deluge. We perform cloud‐resolving simulations in polar night and show that the same transition occurs, implying that some revision of their mechanism is necessary. We perform further tests to show that episodic deluges can occur even if the lower‐tropospheric radiative heating rate is negative, as long as the magnitude of the upper‐tropospheric radiative cooling is about twice as large. We find that in the episodic deluge regime the period can be predicted from the time for radiation and reevaporation to cool the lower atmosphere.

P‐156: Efficiency Improvement Mechanism Analysis of Sidewall Passivation GaN based Micro‐LEDs by Atomic Layer Deposition

Sidewall passivation using atomic layer deposition (ALD) can efficiently improve external quantum efficiency (EQE). Such treatment increases EQE, a combination of internal quantum efficiency (IQE) and light extraction efficiency (LEE), primarily by curtailing surface recombination according to the ABC model. Determined by the ratio of radiative recombination rate to total recombination rate, the IQE of an LED holds a significant correlation with the diode's ideality factor in the Shockley model. In this paper, we analysis the mechanism of ALD sidewall passivation enhancing device performance in detail from the aspects of electrical performance improvement and optical performance improvement.

A Thorough Examination of the Variables Affecting the Quantum Efficiency of Radiative Decay of Trichlorotriphenylmethyl Radicals.

Fluorescence quantum efficiency is determined by the competition between radiation and nonradiation processes of the excited states. Understanding the factors affecting the radiation and nonradiative decay rates is of great significance for the design of luminescent materials. The excitation state deactivation mechanisms of singlet and triplet states have been extensively studied, providing a comprehensive understanding of the processes involved in the relaxation of these states. However, research on free radical systems involving doublet states is relatively scarce. Therefore, in this study, radiation and nonradiative decay rates and the mechanism of a series of trichlorotriphenylmethyl-based radicals were investigated theoretically. The results indicate that the relative rotations of electron donor and acceptor, as well as the internal rotations of trichlorotriphenylmethyl moiety, play important roles in energy dissipation through nonradiative channels. The effect of a solid-state environment on the radiation and nonradiative decay rates of radicals was investigated using a combination of quantum mechanics and molecular mechanics methods. The results indicate that the solid-state environment restricts the expansion of the conjugated system in the excited state of radicals, leading to a slight decrease in radiative decay rate. In addition, the solid-state environment reduces the reorganization energy and also affects the adiabatic excitation energy of radicals. The reduction in reorganization energy results in a decrease in nonradiative rate, while the opposite effect is observed for adiabatic excitation energy. The nonradiative rate of radicals in a solid-state environment is thus inflected by a combination of molecular geometric structure relaxation and ground-excited state energy gap.

Dynamic control of spontaneous emission using magnetized InSb higher-order-mode antennas

We exploit InSb’s magnetic-induced optical properties to design THz sub-wavelength antennas that actively tune the radiative decay rates of dipole emitters at their proximity. The proposed designs include a spherical InSb antenna and a cylindrical Si-InSb hybrid antenna demonstrating distinct behaviors. The former dramatically enhances both radiative and non-radiative decay rates in the epsilon-near-zero region due to the dominant contribution of the Zeeman-splitting electric octupole mode. The latter realizes significant radiative decay rate enhancement via magnetic octupole mode, mitigating the quenching process and accelerating the photon production rate. A deep-learning-based optimization of emitter positioning further enhances the quantum efficiency of the proposed hybrid system. These novel mechanisms are promising for tunable THz single-photon sources in integrated quantum networks.

Efficient Blue Photo- and Electroluminescence from CF3-Decorated Cu(I) Complexes.

Luminescent organometallic complexes of earth-abundant copper(I) have long been studied in organic light-emitting diodes (OLED). Particularly, Cu(I)-based carbene-metal-amide (CMA) complexes have recently emerged as promising organometallic emitters. However, blue-emitting Cu(I) CMA complexes have been rarely reported. Here we constructed two blue-emitting Cu(I) CMA emitters, MAC*-Cu-CF3Cz and MAC*-Cu-2CF3Cz, by introducing one or two CF3 substitutes into carbazole ligands. Both complexes exhibited high thermal stability and blue emission colors. Moreover, two complexes exhibited different emission origins rooting from different donor ligands: a distinct thermally activated delayed fluorescence (TADF) from ligand-to-ligand charge transfer excited states for MAC*-Cu-CF3Cz or a dominant phosphorescence nature from local triplet excited state of the carbazole ligand for MAC*-Cu-2CF3Cz. Inspiringly, MAC*-Cu-CF3Cz had high photoluminescence quantum yields of up to 94 % and short emission lifetimes of down to 1.2 μs in doped films, accompanied by relatively high radiative rates in the 105 s-1 order. The resultant vacuum-deposited OLEDs based on MAC*-Cu-CF3Cz delivered pure-blue electroluminescence at 462 nm together with a high external quantum efficiency of 13.0 %.

Enhanced photoluminescence characteristics in Mg doped Alq3: An insight into doping mechanism

The present paper deals with the investigations on the effect of Mg doping on the structural and photophysical properties of Alq3 thin films. Mg doped Alq3 powders, with varying Mg concentrations, are synthesized using co-precipitation method and their thin films are deposited using vacuum evaporation method. These films are subjected to different analytical analyses to study the effect of Mg doping on the structural and photophysical properties of Alq3. It has been observed that Mg is attached at the central part of the Alq3 molecules making bonds with Al, N and O atoms. In this process, Mg atoms transfer electrons to Alq3 molecules and increases the electron density in its highest occupied molecular orbital (HOMO). Increased HOMO electron density in Mg doped Alq3 results in the improvement in its photoluminescence characteristics. Highest photoluminescent characteristics are observed for Mg doped Alq3 having 1.5 % (by mole) Mg which shows almost 2-fold enhancement in photoluminescence quantum efficiency (PLQY) and 3-fold enhancement in radiative decay rate. The results obtained in this work suggest that Mg doped Alq3 films may be integrated in high performing organic light emitting devices.

Impact of Surrounding Environment on Hot‐Exciton Based Organic Emitters for TADF Applications

AbstractUnderstanding thermally activated delayed fluorescence (TADF) in solid‐state environments is crucial for practical applications. However, limited research focuses on how the medium affects TADF properties of hot‐exciton‐based emitters. In our study, we calculated and compared reverse intersystem crossing, radiative, and non‐radiative decay rates of TADF emitters in gas, solvent, and solid phases. The designed emitters have a donor‐acceptor‐donor (D‐A‐D) structure, with donors such as triphenylamine (TPA) and diphenylamine thiophene (ThPA), combined with acceptors such as benzothiadiazole (BT), pyridine thiadiazole (PT) and thiadiazolobenzopyridine (NPT). We model the solvent and solid phases with the polarizable continuum model (PCM) and quantum mechanical/molecular mechanics (QM/MM) methods, respectively. Using density functional theory (DFT) and time‐dependent DFT, we analyze how TADF emitters′ geometrical, electronic, and excited‐state properties vary in these phases. Our results show that the solid‐state environment significantly influences the geometry and TADF properties of emitters. In the presence of solid medium, our study indicates that non‐radiative decay rates tend to be slower. On the other hand, radiative emission rates were found to be less influenced by the properties of the surrounding medium. Overall, our study connects emitter chemical structure and the surrounding environment‘s impact on excited‐state characteristics and photochemical properties.

Antiprotozoal Pt(II) Complexes as Luminophores Bearing Monodentate P/As/Sb-Based Donors: An X-ray Diffractometric, Photoluminescence, and 121Sb-Mössbauer Spectroscopic Study with TD-DFT-Guided Interpretation and Predictive Extrapolation toward Bi.

In this study, it is demonstrated that the radiative rate constant of phosphorescent metal complexes can be substantially enhanced using monodentate ancillary ligands containing heavy donor atoms. Thus, the chlorido coligand from a Pt(II) complex bearing a monoanionic tridentate C^N*N luminophore ([PtLCl]) was replaced by triphenylphosphane (PPh3) and its heavier pnictogen congeners (i.e., PnPh3 to yield [PtL(PnPh3)]). Due to the high tridentate-ligand-centered character of the excited states, the P-related radiative rate is rather low while showing a significant boost upon replacement of the P donor by heavier As- and Sb-based units. The syntheses of the three complexes containing PPh3, AsPh3, and SbPh3 were completed by unambiguous characterization of the clean products using exact mass spectrometry, X-ray diffractometry, bidimensional NMR, and 121Sb-Mössbauer spectroscopy (for [PtL(SbPh3)]) as well as steady state and time-resolved photoluminescence spectroscopies. Hence, it was shown that the hybridization defects of the Vth main-group atoms can be overcome by complexation with the Pt center. Notably, the enhancement of the radiative rate constants mediated by heavier coligands was achieved without significantly influencing the character of the excited states. A rationalization of the results was achieved by TD-DFT. Even though the Bi-based homologue was not accessible due to phenylation side reactions, the experimental data allowed a reasonable extrapolation of the structural features whereas the hybridization defects and the excited state properties related to the Bi-species and its phosphorescence rate can be predicted by theory. The three complexes showed an interesting antiprotozoal activity, which was unexpectedly notorious for the P-containing complex. This work could pave the road toward new efficient materials for optoelectronics and novel antiparasitic drugs.

Two-Dimensional Electron-Hole Plasma in Colloidal Quantum Shells Enables Integrated Lasing Continuously Tunable in the Red Spectrum.

Combining integrated optical platforms with solution-processable materials offers a clear path toward miniaturized and robust light sources, including lasers. A limiting aspect for red-emitting materials remains the drop in efficiency at high excitation density due to non-radiative quenching pathways, such as Auger recombination. Next to this, lasers based on such materials remain ill characterized, leaving questions about their ultimate performance. Here, we show that colloidal quantum shells (QSs) offer a viable solution for a processable material platform to circumvent these issues. We first show that optical gain in QSs is mediated by a 2D plasma state of unbound electron-hole pairs, opposed to bound excitons, which gives rise to broad-band and sizable gain across the full red spectrum with record gain lifetimes and a low threshold. Moreover, at high excitation density, the emission efficiency of the plasma state does not quench, a feat we can attribute to an increased radiative recombination rate. Finally, QSs are integrated on a silicon nitride platform, enabling high spectral contrast, surface emitting, and TE-polarized lasers with ultranarrow beam divergence across the entire red spectrum from a small surface area. Our results indicate QS materials are an excellent materials platform to realize highly performant and compact on-chip light sources.

Theoretical insights on highly efficient X-shaped near-infrared thermal activation delayed fluorescence emitter

The near-infrared (NIR) thermally activated delayed fluorescence (TADF) molecules hold practical application value in various fields, including biological imaging, anti-counterfeiting, sensors, telemedicine, photomicrography, and night vision display. These molecules have emerged as a significant development direction in organic electroluminescent devices, offering exciting possibilities for future technological advancements. Despite the remarkable potential of NIR-TADF molecules in various applications, the development of molecules that exhibit both long-wavelength emission and high efficiency remains a significant challenge. Herein, based on T-type and Y-type TADF molecules BCN-TPA and ECN-TPA, a novel X-type TADF molecule X-ECN-TPA is theoretically designed through a molecular fusion strategy. Utilizing first-principles calculations and the thermal vibration correlation function (TVCF) method, the photophysical properties and luminescent mechanisms of these three molecules in both solvent and solid (doped films) are revealed. A comparison of the luminescent properties of isomeric BCN-TPA and ECN-TPA shows that the enhanced luminescence efficiency of BCN-TPA in the solid states is attributed to higher radiative rates and lower non-radiative rates. Furthermore, compared to BCN-TPA and ECN-TPA, X-ECN-TPA exhibits significant conjugation extension, resulting in a pronounced redshift, reaching 831 nm and 813 nm in solvent and solid states, respectively. Importantly, molecular fusion significantly increases the transition dipole moment density between the donor and acceptor, leading to a substantial increase in radiative transition rates. Additionally, molecular fusion effectively reduces the energy gap between the first singlet excited state (S1) and the first triplet excited state (T1), facilitating the improvement of the reverse intersystem crossing (RISC) process. In addition, the calculation of Marcus formula shows that the triplet energy transfer from CBP to BCN-TPA, ECN-TPA and X-ECN-TPA is very effective. This work not only designs a novel efficient NIR-TADF molecule but also proposes a strategy for designing efficient NIR-TADF molecules. This principle offers unique insights for optimizing traditional molecular frameworks, opening up new possibilities for future advancements.

Theoretical study on the differences in donor‐acceptor interaction and electron transition mechanism in Pd(II) and Pt(II) complexes

AbstractThe relativistic effect enhances spin‐orbit coupling (SOC), making metal complexes potential candidates for phosphorescent OLED emitters. However, the relativistic effect profoundly influences the donor and acceptor interactions (D‐A), resulting in unique electron transition processes. By stabilizing the s orbitals and destabilizing the d orbitals of the center metal atom, the relativistic effect enhances donation, back donation, and the trans effect in PtN1N more than in PdN1N. Particularly, the back donation in PtN1N is approximately four times greater than that in PdN1N, contributing to the greater stability and rigidity in PtN1N. Furthermore, the relativistic effect enhances the SOC and reduces the excitation energy and stabilizes the excited states of PtN1N. Consequently, the radiative decay rate and non‐radiative rate are accelerated simultaneously. The reverse intersystem crossing rate in PdN1N is accelerated by high temperature, which is responsible for thermally activated delayed fluorescence (TADF).

Deep-Blue and Fast Delayed Fluorescence from Carbene-Metal-Amides for Highly Efficient and Stable Organic Light-Emitting Diodes.

Linear gold complexes of the "carbene-metal-amide" (CMA) type are prepared with a rigid benzoguanidine amide donor and various carbene ligands. These complexes emit in the deep-blue range at 424 and 466nm with 100% quantum yields in all media. The deep-blue thermally activates delayed fluorescence originates from a charge transfer state with an excited state lifetime as low as 213ns, resulting in fast radiative rates of 4.7×106s-1. The high thermal and photo-stability of these carbene-metal-amide (CMA) materials enabled the authors to fabricate highly energy-efficient organic light-emitting diodes (OLED) in host-guest architectures. Deep-blue OLED devices with electroluminescence at 416 and 457nm with practical external quantum efficiencies of up to 23% at 100cdm-2 with excellent color coordinates CIE (x; y)=0.16; 0.07 and 0.17; 0.18 are reported. The operating stability of these OLEDs is the longest reported to date (LT50=1h) for deep-blue CMA emitters, indicating a high promise for further development of blue OLED devices. These findings inform the molecular design strategy and correlation between delayed luminescence with high radiative rates and CMA OLED device operating stability.