Decrease In Photoluminescence Quantum Yield Research Articles

Synergistic ligand mediated anion exchange of CsPbI3 quantum dots for high performance white LED and anti‐counterfeiting

AbstractAnion exchange is an effective strategy to regulate the composition and optoelectronic properties of perovskite quantum dots (PQDs). Though promising, it is more desirable to synthesize PQDs to avoid the decrease of photoluminescence quantum yield (PLQY). Herein, we developed a ligand mediated anion exchange approach, in which the phase transition from CsPbBr3 QDs to CsPbI3 QDs was observed with the introduction of N‐Acetyl‐l‐cysteine (NAC) and 1,3‐dimethylimidazolium iodide (DMII) aqueous solution in CsPbBr3 QDs solution. NAC is expected to create more halogen vacancies in CsPbBr3 QDs, which provides sufficient adsorption sites for I− ions, resulting in accelerating the anion exchange rate in the process of DMII incorporation. Benefiting from the synergistic ligand mediated anion exchange, high PLQY of 97% and remarkable stability of CsPbI3 QDs are obtained. Furthermore, a white light‐emitting diode (WLED) with a lumen efficiency (LE) of 116.82 lm/W is constructed, showing remarkable stability under continuous operation.image

Elucidating the Role of Antisolvents on the Surface Chemistry and Optoelectronic Properties of CsPbBrxI3-x Perovskite Nanocrystals.

Colloidal lead-halide perovskite nanocrystals (LHP NCs) have emerged over the past decade as leading candidates for efficient next-generation optoelectronic devices, but their properties and performance critically depend on how they are purified. While antisolvents are widely used for purification, a detailed understanding of how the polarity of the antisolvent influences the surface chemistry and composition of the NCs is missing in the field. Here, we fill this knowledge gap by studying the surface chemistry of purified CsPbBrxI3-x NCs as the model system, which in itself is considered a promising candidate for pure-red light-emitting diodes and top-cells for tandem photovoltaics. Interestingly, we find that as the polarity of the antisolvent increases (from methyl acetate to acetone to butanol), there is a blueshift in the photoluminescence (PL) peak of the NCs along with a decrease in PL quantum yield (PLQY). Through transmission electron microscopy and X-ray photoemission spectroscopy measurements, we find that these changes in PL properties arise from antisolvent-induced iodide removal, which leads to a change in halide composition and, thus, the bandgap. Using detailed nuclear magnetic resonance (NMR) and Fourier-transform infrared spectroscopy (FTIR) measurements along with density functional theory calculations, we propose that more polar antisolvents favor the detachment of the oleic acid and oleylamine ligands, which undergo amide condensation reactions, leading to the removal of iodide anions from the NC surface bound to these ligands. This work shows that careful selection of low-polarity antisolvents is a critical part of designing the synthesis of NCs to achieve high PLQYs with minimal defect-mediated phase segregation.

Excitation-Energy-Dependent Photoluminescence Quantum Yield is Inherent to Optically Robust Core/Alloy-Shell Quantum Dots in a Vast Energy Landscape.

The importance of alloy-shelling in optically robust Core/Alloy-Shell (CAS) QDs has been described from structural and energetic aspects. Unlike fluorescent dyes, both Core/Shell (CS) and CAS QDs exhibit excitation-energy-dependent photoluminescence quantum yield (PLQY). For both CdSe and InP CAS QDs (with metal- and nonmetal-based alloy-shelling, respectively), with increasing excitation energy, (a) the ultrafast rise-time or relaxation-time to the band-edge increases and (b) the magnitude of the normalized bleach signal decreases. Ultrasensitive single-particle spectroscopic investigation results showed that with decreasing excitation energy, (a) the fraction of ON events increases, (b) the ratio of exciton-detrapping rate/trapping rate increases, and (c) the extent of beneficial hole trapping increases. A relative decrease in PLQY with increasing excitation energy is much less pronounced in CAS QDs than in CS QDs. Unless trap states are removed completely especially in the higher-energy landscape, PLQY will remain inherently dependent on excitation energy for QDs in the vast energy landscape. When reporting the PLQY of QDs, the magnitude of the excitation energy must be mentioned.

Photoluminescence of P3HT:PCBM bulk heterojunction thin films and effect of external electric field

AbstractSteady‐state and time‐resolved photoluminescence (PL) and electrophotoluminescence (E‐PL) have been recorded for bulk heterojunction samples of thin films of regio‐regular poly(3‐hexylthiophene) (P3HT) and methyl [6,6]‐phenyl‐C61‐butanoate (PCBM). The PL spectra of the bulk heterojunction samples showed a monotonic decrease of PL quantum yield with increased PCBM content in the film. The PL decay was measured with both a femtosecond up‐conversion technique and a time‐correlated single‐photon‐counting technique. The mechanism of PL quenching deviated from a simple Stern‐Volmer equation, explained in terms of an apparent static quenching with a sphere‐of‐action model and dynamic quenching. With increased content of PCBM, the static quenching played a dominant role. Upon application of an electric field, the E‐PL spectra of both P3HT and bulk heterojunction samples showed an enhanced quantum yield and incremented lifetime of PL of P3HT. The long‐range electron transfer from P3HT to PCBM was retarded upon application of an electric field; the field‐induced change increased with increasing PCBM content.

Solvatochromic and solid-state emissive azlactone-based AIEE-active organic dye: Synthesis, photophysical properties and color-conversion LED application

Here, we report one-pot synthesis of a new azlactone-based dye bearing isoxazole moiety as a donor group (i.e., Dye-Iso), which displays fluorescence emission both in solution and solid-state, and a systematic study of its photophysical properties. The analyses of steady-state photoluminescence (PL) spectroscopy measurements reveal that Dye-Iso exhibits positive solvatochromic behavior accompanied by the decreasing trend in PL quantum yield (QY), as the polarity of solvent increases. In addition, time-resolved fluorescence (TRF) spectroscopy shows that the PL lifetime is shortening and overall effective nonradiative decay rate becomes accelerated with increasing polarity of the medium, which explain well the decrease in PL QY. These findings strongly suggest that the dipole-dipole interactions between the dye molecule having intramolecular charge transfer (ICT) characteristic and solvent are responsible for the redshift in PL emission with the increase in solvent polarity. Furthermore, the electronically ground- and excited-state dipole moments were determined by using linear correlation methods having different solvent polarity functions. The results depict that the Dye-Iso has a larger excited-state dipole moment as against that in the ground-state, which reflects the ICT mechanism. The spectroscopic studies show that the Dye-Iso exhibits aggregation-induced emission enhancement (AIEE) under aggregate formation and is AIEE-active compound. The PL QYs of the Dye-Iso in aggregation- and solid-state were also found to be higher in comparison with those in solutions, which has been elucidated by the increase in the radiative decay rate due to restriction of intramolecular motions (RIM). Finally, we have demonstrated that the AIEE-active Dye-Iso can be used as a color-conversion material for solid-state lighting applications by employing that on a commercial near-ultraviolet LED.

Highly Luminescent and Water-Resistant CsPbBr3–CsPb2Br5 Perovskite Nanocrystals Coordinated with Partially Hydrolyzed Poly(methyl methacrylate) and Polyethylenimine

All inorganic lead halide perovskite nanocrystals (PNCs) typically suffer from poor stability against moisture and UV radiation as well as degradation during thermal treatment. The stability of PNCs can be significantly enhanced through polymer encapsulation, often accompanied by a decrease of photoluminescence quantum yield (PLQY) due to the loss of highly dynamic oleylamine/oleic acid (OLA/OA) ligands. Herein, we propose a solution for this problem by utilizing partially hydrolyzed poly(methyl methacrylate) (h-PMMA) and highly branched poly(ethylenimine) (b-PEI) as double ligands stabilizing the PNCs already during the mechanochemical synthesis (grinding). The hydrophobic polymer of h-PMMA imparts excellent film-forming properties and water stability to the resulting NC-polymer composite. In its own turn, the b-PEI forms an amino-rich, strongly binding ligand layer on the surface of the PNCs being responsible for the significant improvement of the PLQY and the stability of the resulting material. Moreover, the introduction of b-PEI promotes a partial phase conversion from CsPbBr3 to CsPb2Br5 to obtain CsPbBr3/CsPb2Br5 nanocrystals with a core-shell-like structure. As-prepared PNCs solutions are directly processable as inks, while their PLQY drops only slightly from 75% in colloidal solution to 65% in films. Moreover, the final PNC-polymer film exhibits excellent stability against water, heat, and ultraviolet light irradiation. These superior properties allowed us to fabricate a proof of concept thin film OLED with h-PMMA/b-PEI-stabilized PNCs as an easily processable, narrowly emitting color conversion composite material.

Photostability and Photodegradation Processes in Colloidal CsPbI3 Perovskite Quantum Dots

All-inorganic CsPbI3 perovskite quantum dots (QDs) have attracted intense attention for their successful application in photovoltaics (PVs) and optoelectronics that are enabled by their superior absorption capability and great photoluminescence (PL) properties. However, their photostability remains a practical bottleneck and further optimization is highly desirable. Here, we studied the photostability of as-obtained colloidal CsPbI3 QDs suspended in hexane. We found that light illumination does induce photodegradation of CsPbI3 QDs. Steady-state spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and transient absorption spectroscopy verified that light illumination leads to detachment of the capping agent, collapse of the CsPbI3 QD surface, and finally aggregation of surface Pb0. Both dangling bonds containing surface and Pb0 serve as trap states causing PL quenching with a dramatic decrease of PL quantum yield. Our work provides a detailed insight about the correlation between the structural and photophysical consequences of the photodegradation process in CsPbI3 QDs and may lead to the optimization of such QDs toward device applications.

Controlled optical properties of water-soluble CdTe nanocrystals via anion exchange

We report a study on anion exchange reaction of CdTe nanocrystals with S2− in aqueous solution under ambient condition. We found that the optical properties of CdTe nanocrystals can be well tuned by controlling the reaction conditions, in which the reaction temperature is crucially important. At low reaction temperature, the product nanocrystals showed blue-shifts in both absorption and PL spectra, while the photoluminescence quantum yield (PLQY) was significantly enhanced. When anion exchanges were carried out at higher reaction temperature, on the other hand, obvious red shifts in absorption and PL spectra accompanied by a fast increase followed by gradual decrease in PLQY were observed. On variation of S2− concentration, it was found that the overall kinetics of Te2− for S2− exchanges depends also on [S2−] when anion exchanges were performed at higher temperature. A possible mechanism for anion exchanges in CdTe NCs was proposed.

Correlation of photoluminescent quantum efficiency and device characteristics for the soluble electrophosphorescent light emitter with interfacial layers

We have investigated the effects of interfacial layers on the properties of soluble phosphorescent organic light emitting devices. Two kinds of polyfluorene-based interfacial layer materials have been studied; both were spin coated on top of PEDOT:PSS to form the insoluble layers by thermal annealing. The molecular-doped, phosphorescent light emitting layer comprising a polymeric host, small molecular host, and guest molecule was fabricated onto the thin interfacial layer. The photoluminescence quantum yield (PLQY) of these layers was measured with an integrating sphere. We have calculated the PLQY values of the single phosphorescent light emitting layer and various organic multilayers incorporating the interfacial layers, showing that a reduction in PLQY due to the interfacial quenching is more significant in the thicker interfacial layer structures. In spite of the decrease in PLQY induced by the triplet energy mismatch, polyfluorene-based interfacial layers improved the charge injection from PEDOT:PSS to the emitting layer, which results in the enhanced brightness and current. The triplet quenching by the interfacial layer could explain the reduction in luminous efficiency of the devices compared to the reference. This was also investigated by studying the charge carrier trapping, change in the spectral characteristics induced by the shift in the emission zone, and the analysis on the carrier balance of devices.

Investigating the Effect of Steric Crowding in Phosphorescent Dendrimers

A simple convergent procedure has been developed for the formation of sterically encumbered phosphorescent dendrimers. The procedure is demonstrated with the preparation of a first-generation dendrimer composed of a fac-tris(2-phenylpyridyl)iridium(III) core and three dendrons. Each dendron is comprised of a branching phenyl unit with a further four phenyl groups attached. The lack of surface groups on the dendrons was found to reduce solubility and also reduced the level of control over the intermolecular interactions of the emissive and electroactive core in films. The 6-fold decrease in photoluminescence quantum yield in going from solution (69%) to the solid state (11%) showed that there were strong intermolecular interactions of the emissive cores in the solid state. Single-layer devices with the dendrimer blended with 4,4‘-bis(N-carbazolyl)biphenyl showed an external quantum efficiency of 1.7% (5.4 cd/A) at 100 cd/m2 and 11.4 V, giving a power efficiency of 1.5 lm/W.

Fully Spiro-Configured Terfluorenes as Novel Amorphous Materials Emitting Blue Light

A series of fully spiro-configured terfluorenes were synthesized and characterized to be amorphous materials showing a Tg of 296 °C with dendritic aromatic pendants, the highest value ever reported for organic molecular systems. X-ray single-crystal analysis of key structural moieties indicated nearly perpendicular orientations at all spiro-links. The spectroscopic comparison of solid film and dilute solution suggested absence of aggregates in the ground state and no increase in torsion angle with an increasing volume of the aromatic pendant. All these conformational characteristics are consistent with molecular mechanics simulation. Thermal annealing in argon caused a decrease in photoluminescence quantum yield with phenyl pendants but an increase with dendritic pendants. These can be understood in terms of local morphological reorganization of molecules to enhance or inhibit interactions between the backbone chromophores.