Fabrication of Potassium- and Rubidium-Doped Formamidinium Lead Bromide Nanocrystals for Surface Defect Passivation and Improved Photoluminescence Stability.

The past decade has seen a rapid development in metal halide perovskite nanocrystals (NCs), which has been witnessed by their potential applications in nanotechnology. The inimitable chemical nature behind their unique photoluminescence characteristics has attracted a growing body of researchers. However, the low intrinsic stability and surface defects of perovskite NCs have hampered their widespread applications. Therefore, numerous techniques such as doping and encapsulation (polymer matrices, silica coating, salt matrix, etc.) have been examined for the surface modification of perovskite NCs and to increase their efficiency and stability. In this study, we demonstrated the self-passivation method for surface defects by introducing potassium (K) or rubidium (Rb) during the colloidal fabrication of NCs, resulting in the much-improved crystallinity, photoluminescence, and improved radiative efficiency. In addition, K-doped NCs showed a long-term colloidal stability of more than 1 month, which indicates the strong bonding between the NCs and the smaller-sized potassium cations (K+). We observed the enhancement of the radiative lifetime that can also be explained by the prevention of "Frenkel defects" when K+ stays at the interstitial site of the nanocrystal structure. Furthermore, our current findings signify the importance of surface modification techniques using alkali metal ions to reduce the surface traps of perovskite nanocrystals (PeNCs). Comparable developments could be applied to polycrystalline perovskite thin films to reduce the interface trap densities. The findings of this study have several important implications for future light-emitting applications.

Organic Holmium(III) Complexes as a Potential Bright Emitter in Thin Films.

Holmium(III) ions incorporated with an organic ligand generate ∼2 µm optical emission which is characterized by steady and time-resolved photoluminescence. A potential efficient sensitization scheme is demonstrated by empirically calculating the Förster energy transfer rate and modeling the excited state dynamics of the ion. This is demonstrated by taking into account an ideal organic chromophore. The presented work proposes a promising material candidate for the 2 µm emission, which can be fabricated in thin films.

Bright and Efficient Sensitized Near-Infrared Photoluminescence from an Organic Neodymium-Containing Composite Material System.

Intense organic neodymium (Nd3+) emission is obtained with near-infrared (NIR) emission equivalent in intensity to that of an organic semiconductor emitting material. The advantage of Nd3+ emission is its narrow line width and NIR emission, which is enhanced by ∼3000 times at low excitation power through an efficient sensitization effect from a composite organic sensitizer. This performance is optimized at high concentrations of Nd3+ ions, and the organic perfluorinated system provides the ion excitations with a quantum efficiency of ∼40%. The material system is applicable to thin films that are compatible with integrated optics applications.

Manipulation of Molecular Vibrations on Condensing Er3+ State Densities for 1.5 µm Application.

Vibrational modes of chemical bonds in organic erbium (Er3+) materials play an important role in determining the efficiency of the 1.5 µm Er3+ emission. This work studies the energy coupling of the Er3+ intra-4f transitions and vibrational modes. The results demonstrate that the coupling introduces enormous nonradiative internal relaxation, which condenses the excited erbium population on to the 4I13/2 state. This suggests that vibrational modes can be advantageous for optimizing the branching ratio for the 1.5 µm transition in organic erbium materials. Through control of the quenching effect on to the 4I13/2 state and a reliable determination of intrinsic radiative rates, it is found that the pump power for population inversion can be reduced by an order of magnitude at high erbium concentrations compared to conventional inorganic erbium materials.

Efficient and Stable Perovskite Solar Cells with a Superhydrophobic Two-Dimensional Capping Layer.

A two-dimensional (2D) perovskite layer is considered to be a desirable defect passivation structure for the lifelong stability of perovskite solar cells (PSCs). However, the efficiency could be compromised behind the traditional PSCs. Herein, we solve this issue by employing a highly hydrophobic organic cation, 2-[4-(trifluoromethyl)phenyl]ethanamine (CF3-PEA), to form a 2D (CF3-PEA)2PbI4 to effectively passivate the 3D MAPbI3 with fewer defects. The new 2D/3D-structured PSCs show reduced charge recombination, an elongated carrier lifetime, efficient charge generation and transport. Those excellent characters lead to a significant enhancement of the efficiency from 17.9% for pristine PSCs to 21.43% for 2D/3D PSCs. Benefiting from the high hydrophobicity of CF3-PEA, the cells show remarkably improved stability by maintaining 83% of the original efficiency exposed to 80% R.H. and 50 °C for 600 h and 87% under 1 sun illumination for 600 h, which makes our PCSs among the most efficient and stable MAPbI3 solar cells.

Enhanced 1.54-µm photo- and electroluminescence based on a perfluorinated Er(III) complex utilizing an iridium(III) complex as a sensitizer.

Advanced 1.5-µm emitting materials that can be used to fabricate electrically driven light-emitting devices have the potential for developing cost-effective light sources for integrated silicon photonics. Sensitized erbium (Er3+) in organic materials can give bright 1.5-µm luminescence and provide a route for realizing 1.5-µm organic light emitting diodes (OLEDs). However, the Er3+ electroluminescence (EL) intensity needs to be further improved for device applications. Herein, an efficient 1.5-µm OLED made from a sensitized organic Er3+ co-doped system is realized, where a "traditional" organic phosphorescent molecule with minimal triplet-triplet annihilation is used as a chromophore sensitizer. The chromophore provides efficient sensitization to a co-doped organic Er3+ complex with a perfluorinated-ligand shell. The large volume can protect the Er3+ 1.5-µm luminescence from vibrational quenching. The average lifetime of the sensitized Er3+ 1.5-µm luminescence reaches ~0.86 ms, with a lifetime component of 2.65 ms, which is by far the longest Er3+ lifetime in a hydrogen-abundant organic environment and can even compete with that obtained in the fully fluorinated organic Er3+ system. The optimal sensitization enhances the Er3+ luminescence by a factor of 1600 even with a high concentration of the phosphorescent molecule, and bright 1.5-µm OLEDs are obtained.

Standardized Auricular Therapy for Patients with Different Constitutions and Suboptimal Health: A Retrospective Study.

Objective: According to the guideline for preventive treatment in Traditional Chinese Medicine (TCM), this study examined the efficacy of standardized auricular therapy for patients with different constitutions who had suboptimal health. To prevent the occurrence and development of diseases, it is necessary to find new positive and feasible methods. Materials and Methods: A retrospective study of standardized auricular therapy for patients with different constitutions who had suboptimal health was conducted. The study included 176 patients with Qi Deficiency, Yang Deficiency, Yin Deficiency, Qi Stagnation, Phlegm Dampness, Blood Stasis, Damp-Heat, and Special Constitution. As the patients underwent treatment, they were examined with a weekly test for changes in symptoms for 4 weeks. Results: Using statistical analysis, the efficacy rate of treatment for patients with Yang deficiency was 83.90%. Other constitutional efficacy rates were: Yin Deficiency, 84.62%; Qi Deficiency, 75.00%; Qi Stagnation, 92.31%; Phlegm-Dampness, 82.69%; Damp-Heat, 84.84%; Blood Stasis, 71.43%; and Special Endowment, 83.33%. Conclusions: Standardized auricular therapy has curative effects on patients with a variety of constitutions and who have suboptimal health. This therapy can not only balance the constitutions of patients with suboptimal health but also can play an important role in the field of prevention and health-promoting medicine.

Enhanced deep-red emission from Mn4+/Mg2+ co-doped CaGdAlO4 phosphors for plant cultivation.

Mn4+-Doped oxide phosphors are under intensive investigation owing to their low manufacture cost and attractive luminescent features for indoor plant cultivation applications. However, it is still a challenge to develop Mn4+-doped oxides with high luminescence efficiency and thermal stability. Herein, Mn4+-Mg2+ pairs are incorporated into a CaGdAlO4 host to reduce non-radiative channels formed by Mn4+-Mn4+-O2- clusters. The photoluminescence and quantum efficiency are significantly enhanced after the introduction of Mg2+ ions to the host. A prolonged Mn4+ decay time is also obtained from the Mn4+/Mg2+ co-doped samples. Intense red emission with a narrow peak at 712 nm due to the 2Eg → 4A2g transition of Mn4+ ions is observed under 335 nm excitation. LEDs fabricated by coating the synthesized phosphor on a 365 nm near-UV chip exhibit an intense deep-red emission with CIE chromaticity coordinates of (0.712, 0.285). The results indicate Mn4+/Mg2+ co-doped CaGdAlO4 phosphors may be applicable to plant cultivation fields.

NIR Downconversion and Energy Transfer Mechanisms in Tb3+/Yb3+ Codoped Na5Lu9F32 Single Crystals.

Tb3+/Yb3+ codoped Na5Lu9F32 single crystals with near-infrared (NIR) emission are achieved by an improved Bridgman approach. Energy transfer from Tb3+ to Yb3+ ions is affirmed by the photoluminescence (PL) emission spectra and decay curves characterization. On the basis of the analysis of energy transfer rate dependence on the Yb3+ concentration, the interaction between Tb3+ and Yb3+ ions in Na5Lu9F32 single crystals is confirmed through the one-to-one energy transfer process. Results demonstrate that the prepared Na5Lu9F32 single crystals might be promising candidates to convert sunlight to improve the performance of the silicon solar cells.

Continuous Tuning of Organic Phosphorescence by Diluting Triplet Diffusion at the Molecular Level.

Organic long-persistent phosphorescent materials are advantageous due to the cost-effectiveness and easy processability. The organic phosphorescence is achieved by the long-lived triplet excitons, and the challenges are recognized regarding the various nonradiative pathways to quench the emission lifetime. Taming long-lived phosphorescence is generally engaged with the charge-transfer or exciton diffusion in molecular stacking to stabilize triplet excitons or form a photoinduced ionized state. Herein, we elucidate that the triplet-diffusion can cause a significant quenching that is not thermally activated by using a system of perfluorinated organic complexes. Hence, we suggest a coevaporation technique to dilute a single phosphorescence-emitting molecule with another optically inactive molecule to suppress the diffusion-induced quenching, tuning the phosphorescence lifetime and spectral features continuously. The work successfully suggests a general semitheoretical method of quantifying the population equilibrium to elucidate the loss mechanisms for organic phosphorescence.

Molecular-Barrier-Enhanced Aromatic Fluorophores in Cocrystals with Unity Quantum Efficiency.

Singlet-triplet conversion in organic light-emitting materials introduces non-emissive (dark) and long-lived triplet states, which represents a significant challenge in constraining the optical properties. There have been considerable attempts at separating singlets and triplets in long-chain polymers, scavenging triplets, and quenching triplets with heavy metals; nonetheless, such triplet-induced loss cannot be fully eliminated. Herein, a new strategy of crafting a periodic molecular barrier into the π-conjugated matrices of organic aromatic fluorophores is reported. The molecular barriers effectively block the singlet-to-triplet pathway, resulting in near-unity photoluminescence quantum efficiency (PLQE) of the organic fluorophores. The transient optical spectroscopy measurements confirm the absence of the triplet absorption. These studies provide a general approach to preventing the formation of dark triplet states in organic semiconductors and bring new opportunities for the development of advanced organic optics and photonics.

Bright Photon Upconversion on Composite Organic Lanthanide Molecules through Localized Thermal Radiation.

Converting low-energy photons via thermal radiation can be a potential approach for utilizing infrared (IR) photons to improve photovoltaic efficiency. Lanthanide-containing materials have achieved great progress in IR-to-visible photon upconversion (UC). Herein, we first report bright photon, tunable wavelength UC through localized thermal radiation at the molecular scale with low excitation power density (<10 W/cm2) realized on lanthanide complexes of perfluorinated organic ligands. This is enabled by engineering the pathways of nonradiative de-excitation and energy transfer in a composite of ytterbium and terbium perfluoroimidodiphosphinates. The IR-excited thermal UC and wavelength control is realized through the terbium activators sensitized by the ytterbium sensitizers having high luminescence efficiency. The metallic molecular composite thus can be a potential energy material in the use of the IR solar spectrum for thermal photovoltaic applications.

Sensitization, energy transfer and infra-red emission decay modulation in Yb3+-doped NaYF4 nanoparticles with visible light through a perfluoroanthraquinone chromophore.

Infra-red emission (980 nm) of sub 10 nm Yb3+-doped NaYF4 nanoparticles has been sensitized through the excitation of 2-hydroxyperfluoroanthraquinone chromophore (1,2,3,4,5,6,7-heptafluro-8-hydroxyanthracene-9,10-dione) functionalizing the nanoparticle surface. The sensitization is achieved with a broad range of visible light excitation (400-600 nm). The overall near infra-red (NIR) emission intensity of Yb3+ ions is increased by a factor 300 as a result of the broad and strong absorption of the chromophore compared with ytterbium's intrinsic absorption. Besides the Yb3+ NIR emission, the hybrid composite shows organic chromophore-based visible emission in the orange-red region of the spectrum. We observe the energy migration process from the sensitized Yb3+ ions at the surface to those in the core of the particle using time-resolved optical spectroscopy. This highlights that the local environments for emitting Yb3+ ions at the surface and center of the nanoparticle are not identical, which causes important differences in the NIR emission dynamics. Based on the understanding of these processes, we suggest a simple strategy to control and modulate the decay time of the functionalized Yb3+-doped nanoparticles over a relatively large range by changing physical or chemical parameters in this model system.

Visible-Range Sensitization of Er(3+)-Based Infrared Emission from Perfluorinated 2-Acylphenoxide Complexes.

Five new fully fluorinated acylphenoxide ligands, which are aromatic analogues of ß-diketonates, provide visible photosensitization of the Er(3+4)I13/2 → (4)I15/2 emission at ∼1540 nm (of interest for telecommunications) via the "antenna effect", as observed in Cs[ErL4] compounds. Depending on the chemical functionalization, the excitation wavelength can be tuned in the 400-650 nm range. Decay times for the solids are in the range of 7-16 µs, proving that the complexes can be of interest for a number of optoelectronic and photonic applications.

Luminescent zinc(II) complexes of fluorinated benzothiazol-2-yl substituted phenoxide and enolate ligands.

Zn(II) complexes of the following new, fluorine-containing, benzothiazole-derived ligands have been synthesized and characterized crystallographically: 2-(3,3,3-trifluoro-2-oxopropyl)benzothiazole (3), 4,5,6,7-tetrafluoro-2-(3,3,3-trifluoro-2-oxopropyl)benzothiazole (4), 4,5,6,7-tetrafluoro-2-(2-hydroxyphenyl)benzothiazole (12), 2-(3,4,5,6-tetrafluoro-2-hydroxyphenyl)-4,5,6,7-tetrafluorobenzothiazole (13), and 2-(3,4,5,6-tetrafluoro-2-hydroxyphenyl)benzothiazole (16); the Cu(II) complex of ligand 4 is also reported. These are analogs of the important photo- and electroluminescent material [Zn(BTZ)(2)](2), where H-BTZ = 2-(2-hydroxyphenyl)benzothiazole. DFT calculations indicate that HOMO and LUMO energy levels in these materials are substantially lowered by fluorination. The fluorinated ZnL(2) complexes are mononuclear (in contrast to the dinuclear, nonfluorinated material [Zn(BTZ)(2)](2)). They easily sublime and show broad visible photoluminescence. A common crystallographic feature is the existence of pairs of fluorinated ZnL(2) molecules related by inversion centers, with their π systems facing one another.