High Luminescence Quantum Yield Research Articles

Enhanced stability of the optical responses from all-inorganic perovskite nanocrystals embedded in a synthetic opal matrix

Nanostructured luminescent materials based on perovskite nanocrystals (p-NCs) are attractive since their optical properties can be tuned in a wide spectral range with high luminescence quantum yields and lifetimes, however, they lack stability. In this work, the optical properties of highly luminescent colloidal p-NCs (CsPbX3, where X = Cl/Br, Br, I) embedded in porous opal matrices are presented. It is shown that the photoluminescence of the p-NCs embedded into opal matrices possess increased longtime stability of its spectral and kinetic parameters under ambient conditions. LEDs based on the developed materials show pure color p-NC emission with stability of its parameters. The results of this work may expand the knowledge of interactions between luminescent nanoparticles within multicomponent nanostructured materials for further photonic applications.

Crystal growth and luminescence properties of organic crystal scintillators for α-rays detection

Scintillation and luminescence properties of a novel organic crystal scintillator, 1,4-bis(2-methylstyryl) benzene (bis-MSB), were measured and compared with those of the conventional trans-stilbene organic crystal scintillator. Although trans-stilbene has been used for beta or neutron detection, trans-stilbene cannot be applied at high temperature conditions due to a lower melting point (124 °C). Liquid scintillators or plastic scintillators also cannot be used at high temperature. Usually, bis-MSB has been used as dopant in liquid scintillators to obtain fast scintillation decay and high luminescence quantum yield, and its melting point is 181 °C higher than that of trans-stilbene. In this paper, we focused on bis-MSB in solid state. The bis-MSB and trans-stilbene crystals were grown by the self-seeding vertical Bridgman method using double quartz ampoules. The bis-MSB crystal had the fast decay time of ∼4.2 ns and the increased light yield of ∼12,000 ph/5.5 MeV(α), while trans-stilbene had the decay time of ∼8.5 ns and the light yield of ∼8500 ph/5.5 MeV(α). The photoluminescence quantum yield was almost constant up to 125 °C for bis-MSB and only up to 50 °C for trans-stilbene. We succeeded in obtaining the novel organic crystal scintillator which can operate even at higher temperature up to 125 °C.

Growth, spectroscopy and first laser operation of monoclinic Ho3+:MgWO4 crystal

A monoclinic 0.86 at.% Ho3+:MgWO4 crystal is grown by the Top-Seeded-Solution Growth method. Its spectroscopic properties are studied with polarized light for E || a, b, c. The Ho3+ ion transition probabilities are determined within the modified Judd-Ofelt theory (mJ-O) accounting for the configuration interaction. The intensity parameters are Ω2 = 21.09, Ω4 = 4.42, Ω6 = 2.28 [10–20 cm2] and α = 0.053 [10-4 cm]. The calculated radiative lifetime of the 5I7 state is 6.18 ms. The Stark splitting of the 5I7 and 5I8 multiplets is determined with low-temperature spectroscopy. The absorption, stimulated-emission (SE) and gain cross-sections for the 5I8 ↔ 5I7 transition are derived. Ho3+:MgWO4 features a large Stark splitting of the ground-state (380 cm-1), high maximum σSE of 1.82 × 10–20 cm2 at 2.083 μm, broad gain spectra and high luminescence quantum yield making it suitable for efficient continuous-wave and mode-locked lasers at ∼2.1 μm. First laser operation of Ho3+:MgWO4 crystal is demonstrated at 2.104 μm reaching a slope efficiency of 72%.

Efficient Ytterbium Near-Infrared Luminophore Based on a Nondeuterated Ligand.

A novel molecular ytterbium complex is reported with a new tetradentate ligand based on the 2,2'-bipyridine-6,6'-dicarboxylic acid scaffold. The photophysical properties are investigated, especially with respect to near-infrared luminescence. The ytterbium complex shows a rather high absolute luminescence quantum yield of Φ = 3.0% and a luminescence lifetime of τobs = 72 μs at room temperature in CD3OD solution.

Organic-Inorganic Layered and Hollow Tin Bromide Perovskite with Tunable Broadband Emission.

Recently, layered perovskites attracted great attention for its excellent stability and light-emitting property. However, most of them rely on the toxic element lead and their emission quantum yields are generally low. Here, a unique hollow two-dimensional perovskite was developed in which the organic hexamethylene diamines (C6H18N22+) strongly coupled with distorted tin bromide anions (SnBr64-). This toxic-free low-dimensional tin perovskite exhibits a broadband emission in the visible region with a high luminescence quantum yield of 86%. First-principles calculation indicate the broadband emission is associated with the recombination of self-trapped excitons. And the emission is related to the geometry of tin bromide anions. An ultraviolet light-pumped white light emitting diode with excellent color-rendering index of 94 was fabricated using it together with a commercially available blue phosphor.

Luminescence properties and energy transfer in Ce3+/Tb3+co–doped Y5Si3O12N oxynitride phosphors

A series of Y5Si3O12N:Ce3+ single-doped and Ce3+/Tb3+ co–doped phosphors, as potential candidates for application in tri–chromatic white LEDs, were successfully synthesized by a high temperature solid state reaction method. The addition of Li2CO3 flux (5 wt%) improved the purity of the resultant phosphors and increased their emission intensity. An intense, broad excitation band in the range of 200–400 nm with a peak at 358 nm was recorded, which suits the needs of UV LED chips. Under this excitation wavelength, intense blue emission, which peaked at 439 nm, was recorded in the Ce3+ single-doped phosphors, while two distinct luminescence bands were observed in the Ce3+/Tb3+ co–doped Y5Si3O12N phosphors: a blue one, which peaked at 439 nm and is ascribed to Ce3+ ions, and an efficient green one, which peaked at 549 nm and is assigned to 5D4→7F5 transitions in Tb3+ ions. A high luminescence quantum yield, of 85%, was achieved. The experimental results illustrate that efficient energy transfer can take place from the sensitizer Ce3+ ions to the activator Tb3+ ions in the Ce3+/Tb3+ co–doped Y5Si3O12N phosphors, through predominantly dipole–dipole interactions.

Tunable Hybrid Fano Resonances in Halide Perovskite Nanoparticles.

Halide perovskites are known to support excitons at room temperatures with high quantum yield of luminescence that make them attractive for all-dielectric resonant nanophotonics and meta-optics. Here we report the observation of broadly tunable Fano resonances in halide perovskite nanoparticles originating from the coupling of excitons to the Mie resonances excited in the nanoparticles. Signatures of the photon-exciton (" hybrid") Fano resonances are observed in dark-field spectra of isolated nanoparticles, and also in the extinction spectra of aperiodic lattices of such nanoparticles. In the latter case, chemical tunability of the exciton resonance allows reversible tuning of the Fano resonance across the 100 nm bandwidth in the visible frequency range, providing a novel approach to control optical properties of perovskite nanostructures. The proposed method of chemical tuning paves the way to an efficient control of emission properties of on-chip-integrated light-emitting nanoantennas.

HETEROLAYERS OF ANISOTROPIC α-ZnSe FOR PHOTOSENSORS

The optical, luminescence and electrical properties of α-ZnSe heterolayers obtained by the method of isovalent replacement are investigated. The high quantum yield of luminescence η = 10-12% in the short-wave region is established. The dominant role of excitons annihilation and interband transitions of free charge carriers is revealed. The surface-barrier structures of Ni-α-ZnSe, whose spectral region of photosensitivity is ħω = 2.70-3.75 eV, was made. The hexagonal modification of the structure of the obtained heterolayers causes their polarization properties of reflection and photosensitivity.

Chiral BINAPO-Controlled Diastereoselective Self-Assembly and Circularly Polarized Luminescence in Triple-Stranded Europium(III) Podates.

Chiral lanthanide helical architectures have received intense attentions in recent years because of their potential applications as chiral probes and sensors and as circularly polarized luminescence (CPL) materials. However, stereoselectivity control in the self-assembly of lanthanide helicate is challenging due to the poor stereochemical preference and variable coordination numbers of Ln(III) ions. Herein, we reported the employing chiral ancillary ligand R/S-BINAPO to induce achiral tripodal ligand to form a pair of homochiral lanthanide triple-helical podates [Eu(TTEA)((R/S)-BINAPO); R/S-1] {(R/S)-BINAPO = ( R/ S)-2,2'-bis(diphenylphosphoryl)-1,1'-binaphthyl; TTEA = tris[(4-(4,4,4-trifluoro-1,3-dioxobutyl)-benzamido)ethyl]amine}. X-ray crystallographic analysis for rac-1 reveals that the chirality of BINAPO is transferred during the self-assembly process to give either P or M helical architectures in podates. The 1H and 31P NMR and circular dichroism measurements confirm the diastereopurity of the assemblies in solution. A detailed optical and chiroptical characterization reveals that the luminescent enantiopure podates not only exhibit intense CPL with | glum| values reaching 0.072 but also show high luminescence quantum yields of 32.8%. Our results provide a feasible strategy for designing homochiral helical lanthanide supramolecular architecture and synthesizing excellent CPL materials.

NaYF4 :Yb,Er/NaYF4 Core/Shell Nanocrystals with High Upconversion Luminescence Quantum Yield.

Upconversion core/shell nanocrystals with different mean sizes ranging from 15 to 45 nm were prepared via a modified synthesis procedure based on anhydrous rare-earth acetates. All particles consist of a core of NaYF4 :Yb,Er, doped with 18 % Yb3+ and 2 % Er3+ , and an inert shell of NaYF4 , with the shell thickness being equal to the radius of the core particle. Absolute measurements of the photoluminescence quantum yield at a series of different excitation power densities show that the quantum yield of 45 nm core/shell particles is already very close to the quantum yield of microcrystalline upconversion phosphor powder. Smaller core/shell particles prepared by the same method show only a moderate decrease in quantum yield. The quantum yield of 15 nm core/shell particles, for instance, is reduced by a factor of three compared to the bulk upconversion phosphor at high power densities (100 W cm-2 ) and by approximately a factor of 10 at low power densities (1 W cm-2 ).

Highly sensitive bifunctional sensor of a dinuclear terbium complex

A new dinuclear terbium complex (Tb-complex) is designed and synthesized based on 2,4,5-Trifluoro-3-methoxybenzoic acid (HTFMBA). The exact structure of the Tb-complex is determined to be [Tb2(TFMBA)6(phen)2] (phen = phenanthroline). It crystallizes in the triclinic space group P-1, and it is further characterized by FT-IR, PXRD, EA, TGA and luminescence. Tb-complex shows very high luminescence quantum yield (QY) of 61.5%. Detailed investigation reveals that the Tb-complex is a highly sensitive and selective bifunctional sensor for detecting SO42− and CH3Hg+. Responsive behavior shows the detection has excellent linear relationship between luminescence and the concentration of SO42− and CH3Hg+. The limit of detection (LOD) for detecting SO42− and CH3Hg+ are as low as 5 × 10−7 M and 2.8 × 10−9 M, respectively. This is the first bifunctional sensor that could probe the highly toxic CH3Hg+, and it is the most sensitive chemosensor for detecting CH3Hg+. Further investigation also reveal that the Tb-complex is applicable in sensing SO42− and highly toxic CH3Hg+ in real water samples.

Insights into the luminescent properties of anionic cyclometalated iridium(III) complexes with ligands derived from natural products

AbstractIn the search of remarkable anionic electroluminescent semiconductors to be applied in energy conversion devices such as Light Emitting Electrochemical Cells, we report the electronic, photophysical, and charge injection/transfer properties of a series of cyclometalated iridium(III) complexes through a DFT/TD‐DFT procedure. The proposed semiconductors involve bidentated ligands based on natural products (salicylic acid and boldine), and phenylpyridine and phenylpyrazole as the cyclometalating units. The proposed compounds emit in the range of 446 to 571 nm, where the boldine based compounds have red‐shifted emissions compared to their analogs with salicylic acid. Blue phosphors were obtained by the use of phenylpyrazole units; however, the ligand field is weak in these cases compared to the ligand field exerted by the phenylpyridine ligands. The latter allows the accessibility to the radiationless states for emitters below 495 nm as a result of the increased stability of the metal centered excited states; consequently, the luminescent quantum yield could be decreased. Conversely, the semiconductors with phenylpyridine units show a restricted accessibility to radiationless processes, which could result in emitters with a high luminescent quantum yield and low non‐radiative constants. Finally, the proposed anionic semiconductors show a better balance between hole/electron transfer rate compared to related cationic Ir(III) complexes; while, the easier hole‐electron injection is favored for semiconductors with salicylic acid and phenylpyridine units.

Light-Emitting Halide Perovskite Nanoantennas.

Nanoantennas made of high-index dielectrics with low losses in visible and infrared frequency ranges have emerged as a novel platform for advanced nanophotonic devices. On the other hand, halide perovskites are known to possess high refractive index, and they support excitons at room temperature with high binding energies and quantum yield of luminescence that makes them very attractive for all-dielectric resonant nanophotonics. Here we employ halide perovskites to create light-emitting nanoantennas with enhanced photoluminescence due to the coupling of their excitons to dipolar and multipolar Mie resonances. We demonstrate that the halide perovskite nanoantennas can emit light in the range of 530-770 nm depending on their composition. We employ a simple technique based on laser ablation of thin films prepared by wet-chemistry methods as a novel cost-effective approach for the fabrication of resonant perovskite nanostructures.

Synthesis, properties and structure of borafluorene-based conjugated polymers with kinetically and thermodynamically stabilized tetracoordinated boron atoms

Herein, borafluorene-conjugated polymers with a dibromoborafluorene monomer and various boronic acid ester comonomers are reported. By employing the Suzuki−Miyaura cross-coupling reaction, a series of copolymers was prepared with the boron atoms in tetracoordinated states. Based on comparison to the optical properties of gallafluorene copolymers, higher luminescence quantum yields were obtained from the synthesized borafluorene copolymers due to the weak spin-orbit interaction of boron compared to that of gallium. Additionally, the results from the electrochemical measurements indicated that the electron-withdrawing property of the boron atoms led to stabilization of the lowest unoccupied molecular orbitals (LUMOs) of the borafluorene copolymers. In the X-ray diffraction profiles, significant peaks originating from π−π stacking and assembly of the side chains were observed. The borafluorene copolymers were more crystalline than the gallafluorene polymers. Synthesis and properties of borafluorene-containing conjugated polymers with various comonomers are presented. From the comparison with the gallafluorene copolymers, higher luminescent quantum yields were obtained from the borafluorene copolymers. Additionally, from the electrochemical measurements, it was shown that the electron-withdrawing property of the boron atoms led to the stabilization of LUMOs of the borafluorene copolymers. In the X-ray diffraction profiles, the significant peaks originated from π−π stacking and assembly of the side chains were observed. The borafluorene copolymers were more crystalline materials relative to the gallafluorene polymers.

One-step solvothermal synthesis of high-emissive amphiphilic carbon dots via rigidity derivation.

In nanoscience, amphiphilic carbon dots (ACDs) are of great importance due to their excellent transferability for application in biological sensing, imaging and labelling. However, facile synthetic strategies are still limited, especially for obtaining high-emissive ACDs. Since the development of a high-emissive feature is strongly desired for improving the practical resolution in vivo, here we report a chemical strategy that uses rigid molecules to straightforwardly construct amphiphilic carbon dots (ACDs) with high luminescence quantum yields (QYs). By using 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU), a typical coplanar compound, as the only precursor, well-defined ACDs were prepared via a one-step solvothermal process which exhibited a superior QY of up to 29%, largely superior to those prepared from precursors with less rigid structures. The effect can be mainly attributed to a significant suppression of the competition of non-radiative decay through rigidity derivation. Metal ionic doping during the synthesis resulted in a further improvement of the crystallinity and monodispersity of the materials, with retention of the high-emissive ability. This high-emissive photoluminescence behavior of the ACDs is accompanied with an excitation-wavelength dependence, a high biocompatibility and a low toxicity, which together make the ACDs advantageous for application in multi-channel bioimaging.

Ultrahigh luminescence quantum yield lanthanide coordination polymer as a multifunctional sensor.

The investigation and development of advanced multifunctional and sensitive sensors with high luminescent quantum yield and the capability of detecting different analytes, such as metal ions, is imperative. Due to its inherent properties the lanthanide coordination complex is one candidate for sensing applications, particularly for multifunctional sensors. Herein, we present two series of alkali ion decorated lanthanide coordination polymers (Ln-CPs), which show ultrahigh luminescence quantum yields (QYs) of 77% (1a) and 92% (2a). To the best of our knowledge, 1a represents the first trifunctional lanthanide complex sensor that can simultaneous detect and discriminate three different analytes, namely H+/Cd2+/Cr3+ through a multimode optical response. Furthermore, the limit of detection (LOD) for Cr3+ is an ultralow value of 2.0 × 10-9 M with a sensing time of 2 h, which is comparable to the most sensitive Cr3+ chemosensor. More interestingly, 92% (2a) is an unprecedented luminescence QY among the reported lanthanide coordination complexes.

Low-threshold lasing from colloidal CdSe/CdSeTe core/alloyed-crown type-II heteronanoplatelets.

Colloidal type-II heterostructures are believed to be a promising solution-processed gain medium given their spatially separated electrons and holes for the suppression of Auger recombination and their wider emission tuning range from the visible to near-infrared region. Amplified spontaneous emission (ASE) was achieved from colloidal type-II core/shell nanocrystals several years ago. However, due to the limited charge-transfer (CT) interfacial states and minimal overlap of electron and hole wave functions, the ASE threshold has still been very high. Herein, we achieved ASE through type-II recombination at a lower threshold using CdSe/CdSeTe core/alloyed-crown nanoplatelets. Random lasing was also demonstrated in the film of these nanoplatelets under sub-ns laser-pumping. Through a detailed carrier dynamics investigation using femtosecond transient absorption, steady state, and time-resolved photoluminescence (PL) spectroscopies, we confirmed the type-II band alignment, and found that compared with normal CdSe/CdTe core/crown nanoplatelets (where no ASE/lasing was observed), CdSe/CdSeTe core/alloyed-crown nanoplatelets had a much higher PL quantum yield (75% vs. 31%), a ∼5-fold larger density of type-II charge-transfer states, a faster carrier transfer to interfaces (0.32 ps vs. 0.61 ps) and a slower Auger recombination lifetime (360 ps vs. 160 ps). Compared with CdSe/CdTe nanoplatelets, their counterparts with an alloyed crown boast a promoted charge transfer process, higher luminescence quantum yield, and smaller Auger rate, which results in their excellent application potential in solution-processed lasers and light-emitting devices.

A highly luminescent Eu(iii) complex based on an electronically isolated aromatic ring system with ultralong lifetime.

A luminescent Eu(iii) complex with a large electronically isolated aromatic ring system, Eu(hfa)3(DPPTO)2 (where hfa denotes hexafluoroacetylacetonate and DPPTO denotes 2-diphenylphosphoryltriphenylene), is reported. The light-harvesting efficiency of the Eu(iii) complex was assessed from electronic absorption spectra. Luminescence properties were evaluated from luminescence spectra, excitation spectra, luminescence quantum yields, and luminescence lifetimes. A remarkably brilliant luminescence was observed because of the strong light absorption and the high luminescence quantum yield of the Eu(iii) complex. Density functional theory calculations indicated an electronic separation between the energy-donating large π-conjugated orbital and the energy-accepting Eu(iii) orbital. These findings demonstrate that novel Eu(iii) photophysics can be induced by large electronically isolated aromatic ring systems.

Efficient Sky-Blue Perovskite Light-Emitting Devices Based on Ethylammonium Bromide Induced Layered Perovskites.

Low-dimensional organometallic halide perovskites are actively studied for the light-emitting applications due to their properties such as solution processability, high luminescence quantum yield, large exciton binding energy, and tunable band gap. Introduction of large-group ammonium halides not only serves as a convenient and versatile method to obtain layered perovskites but also allows the exploitation of the energy-funneling process to achieve a high-efficiency light emission. Herein, we investigate the influence of the addition of ethylammonium bromide on the morphology, crystallite structure, and optical properties of the resultant perovskite materials and report that the phase transition from bulk to layered perovskite occurs in the presence of excess ethylammonium bromide. On the basis of this strategy, we report green perovskite light-emitting devices with the maximum external quantum efficiency of ca. 3% and power efficiency of 9.3 lm/W. Notably, blue layered perovskite light-emitting devices with the Commission Internationale de I'Eclairage coordinates of (0.16, 0.23) exhibit the maximum external quantum efficiency of 2.6% and power efficiency of 1 lm/W at 100 cd/m2, representing a large improvement over the previously reported analogous devices.

Modulation of the Emission Mode of a Pt(II) Complex via Intermolecular Interactions.

Compounds with controllable color emissions are potentially useful as photoluminescent materials in imaging and sensing applications. Multimolecular emission can be used realizing variable-color emitters and has been demonstrated in the solid state. However, achieving multimolecular emission in solution is difficult to control. In this study, we used a combination of intermolecular interactions, namely hydrogen bonding and solvophobic effect, to modulate multimolecular emissions. A designed Pt complex demonstrated three emission colors: blue (monomer emission), yellow (emission form hydrogen-bonded dimer), and orange (aggregate emission). All of the emission modes exhibited high luminescence quantum yields, as a result of their uniform assemblies.