Highly Photoluminescent Research Articles

Electrically Conductive Photoluminescent Porphyrin Phosphonate Metal–Organic Frameworks

AbstractHerein, the design and synthesis of a highly photoluminescent and electrically conductive metal–organic framework [Zn{Cu‐p‐H6TPPA}]⋅2 [(CH3)2NH] (designated as GTUB3), which is constructed using the 5,10,15,20‐tetrakis [p‐phenylphosphonic acid] porphyrin (p‐H8TPPA) organic linker, is reported. The bandgap of GTUB3 is measured to be 1.45 and 1.48 eV using diffuse reflectance spectroscopy and photoluminescence (PL) spectroscopy, respectively. The PL decay measurement yields a charge carrier lifetime of 40.6 ns. Impedance and DC measurements yield average electrical conductivities of 0.03 and 4 S m−1, respectively, making GTUB3 a rare example of an electrically conductive 3D metal–organic framework. Thermogravimetric analysis reveals that the organic components of GTUB3 are stable up to 400 °C. Finally, its specific surface area and pore volume are calculated to be 622 m2 g−1 and 0.43 cm3 g−1, respectively, using grand canonical Monte Carlo. Owing to its porosity and high electrical conductivity, GTUB3 may be used as a low‐cost electrode material in next generation of supercapacitors, while its low bandgap and high photoluminescence make it a promising material for optoelectronic applications.

Homogeneous and highly photoluminescent composites based on in-situ formed fluorophores in PVA blends

There is a strong demand for developing a simple, scalable, and transferable method to prepare homogeneous and highly photoluminescent composite for diverse applications. Herein, homogeneous composites were successfully synthesized by thermal annealing blends of polyvinyl alcohol, citric acid, and ethylenediamine. The composites exhibited intensive photoluminescence under excitation around 350 nm. Infrared, nuclear resonance, and optical characterizations suggest that diverse structures involving 5-oxo-1,2,3,5-tetrahydroimidazo-[1,2-α]-pyridine-7-carboxylic acid (IPCA) accounts for the high photoluminescence of the composites.

Solvent regulation synthesis of single-component white emission carbon quantum dots for white light-emitting diodes

Abstract White light-emitting diodes (WLEDs) hold great promise in lighting, display, and visible light communication devices, and single-component white emission carbon quantum dots (SCWE-CQDs) as the key component of WLEDs have many outstanding advantages. However, rapid and efficient synthesis of SCWE-CQDs with high photoluminescence quantum yield (PLQY) and stability remains challenging. Here, we report a novel solvent engineering strategy to obtain highly photoluminescent SCWE-CQDs by controlling the dilution ratios between N,N-dimethylformamide (DMF) and pristine red carbon quantum dots (RCQDs) solution. By optimizing synthesis conditions, the relative PLQY of the SCWE-CQDs solution reached 53%. Morphological, structural, and optical property characterizations indicate that the combined action of the hydrogen bond (HB) effect and the size effect leads to the blue shift of RCQDs, but the HB effect is more dominant than the particle size in causing large spectral shifts. In addition, the WLEDs with high color rendering index of 89 and remarkable reliability were obtained based on the highly photoluminescent SCWE-CQDs. This facile solvent engineering approach for synthesizing tunable emission CQDs will promote the progress of carbon-based luminescent materials for applications in optoelectronic devices.

Synthesis of N, Zn-doped carbon dots for the detection of Fe3+ ions and bactericidal activity against Escherichia coli and Staphylococcus aureus

A simple and one-step microwave digestion method was utilized to synthesize the highly photoluminescent glucosamine derived nitrogen and zinc doped carbon dots (N, Zn-CDs) with a bluish-green luminescence property. The synthesized N, Zn-CDs inherited a good photoluminescence property with a quantum yield of 74% and which were characterized by XPS, XRD, TEM, FT-IR, UV–Vis, and fluorescence spectrometry. More importantly, N, Zn-CDs served as a fluorescence sensor for the detection of Fe3+ ions, under optimal conditions, a good linear relationship was established in the concentration range of 0.25–125 μM. Also, the experimental results showed the detection limit of N, Zn-CDs against Fe3+ was 0.15 μM, this could be a promising assay for sensing Fe3+ ions. Also, the role of zinc doping was explored by conducting the detection under similar experimental conditions in the absence of zinc, and reports revealed that the reason for high photoluminescence was due to the zinc doping. Along with the sensing application, our group had investigated the bactericidal property of synthesized N, Zn-CDs against gram-negative (Escherichia coli), and gram-positive pathogens (Staphylococcus aureus). N, Zn-CDs displayed good bactericidal activity against both pathogens under light conditions, but Escherichia coli, even under the dark condition proved its activity. Besides, the morphology of both the strains was displayed before and after the treatment via a scanning electron microscopic images. Also, a plausible mechanism for bactericidal activity was also explained. The reported synthesis method could provide a novel approach for the design of high photoluminescent N, Zn–CDs with good sensing and bactericidal property towards Fe3+ ions, gram-negative and positive bacterial strains.

Synthesis of Highly Photoluminescent All-Inorganic CsPbX3 Nanocrystals via Interfacial Anion Exchange Reactions

All-inorganic cesium lead halide perovskite CsPbX3 (X = Cl, Br, I) nanocrystals (NCs) have attracted significant attention owing to their fascinating electronic and optical properties. However, researchers still face challenges to achieve highly stable and photoluminescent CsPbX3 NCs at room temperature by the direct-synthesis method. Herein, we synthesize CsPbX3 NCs by a facile and environmentally friendly method, which uses an aqueous solution of metal halides to react with Cs4PbBr6 NCs via interfacial anion exchange reactions and without applying any pretreatment. This method produces monodisperse and air-stable CsPbX3 NCs with tunable spectra covering the entire visible range, narrow photoluminescence emission bandwidth, and high photoluminescence quantum yield (PL QY, 80%). In addition, the chemical transformation mechanism between Cs4PbBr6 NCs and CsPbX3 NCs was investigated. The Cs4PbBr6 NCs were converted to CsPbBr3 NCs first by stripping CsBr, and then, the as-prepared CsPbBr3 NCs reacted with metal halides to form CsPbX3 NCs. This work takes advantage of the chemical transformation mechanism of Cs4PbBr6 NCs and provides an efficient and environmentally friendly way to synthesize CsPbX3 NCs.

Highly Photoluminescent and Environmentally Stable Perovskite Nanocrystals Templated in Thin Self‐Assembled Block Copolymer Films

AbstractOrdered nanostructured crystals of thin organic–inorganic metal halide perovskites (OIHPs) are of great interest to researchers because of the dimensional‐dependence of their photoelectronic properties for developing OIHPs with novel properties. Top‐down routes such as nanoimprinting and electron beam lithography are extensively used for nanopatterning OIHPs, while bottom‐up approaches are seldom used. Herein, developed is a simple and robust route, involving the controlled crystallization of the OIHPs templated with a self‐assembled block copolymer (BCP), for fabricating nanopatterned OIHP films with various shapes and nanodomain sizes. When the precursor solution consisting of methylammonium lead halide (MAPbX3, X = Br−, I−) perovskite and poly(styrene)‐block‐poly(2‐vinylpyridine) (PS‐b‐P2VP) is spin‐coated on the substrate, a nanostructured BCP is developed by microphase separation. Spontaneous crystallization of the precursor ions preferentially coordinated with the P2VP domains yields ordered nanocrystals with various nanostructures (cylinders, lamellae, and cylindrical mesh) with controlled domain size (≈40–72 nm). The nanopatterned OIHPs show significantly enhanced photoluminescence (PL) with high resistance to both humidity and heat due to geometrically confining OIHPs in and passivation with the P2VP chains. The self‐assembled OIHP films with high PL performance provide a facile control of color coordinates by color conversion layers in blue‐emitting devices for cool‐white emission.

Highly Photoluminescent and Stable N-Doped Carbon Dots as Nanoprobes for Hg2+ Detection.

We developed a microreactor with porous copper fibers for synthesizing nitrogen-doped carbon dots (N-CDs) with a high stability and photoluminescence (PL) quantum yield (QY). By optimizing synthesis conditions, including the reaction temperature, flow rate, ethylenediamine dosage, and porosity of copper fibers, the N-CDs with a high PL QY of 73% were achieved. The PL QY of N-CDs was two times higher with copper fibers than without. The interrelations between the copper fibers with different porosities and the N-CDs were investigated using X-ray photoelectron spectroscopy (XPS) and Fourier Transform infrared spectroscopy (FTIR). The results demonstrate that the elemental contents and surface functional groups of N-CDs are significantly influenced by the porosity of copper fibers. The N-CDs can be used to effectively and selectively detect Hg2+ ions with a good linear response in the 0~50 μM Hg2+ ions concentration range, and the lowest limit of detection (LOD) is 2.54 nM, suggesting that the N-CDs have great potential for applications in the fields of environmental and hazard detection. Further studies reveal that the different d orbital energy levels of Hg2+ compared to those of other metal ions can affect the efficiency of electron transfer and thereby result in their different response in fluorescence quenching towards N-CDs.

Highly Photoluminescent Sulfide Clusters Confined in Zeolites

The design, synthesis and photoluminescence characterization of sulfide cluster-based zeolitic materials with the general formula Na8[SiAlO4]6SxCl2–2x is presented in this report. The employed experimental conditions, which included the thermal treatment of sodium Linde type A (Na-LTA) zeolites in the presence of Na2SO4 and NaCl, yielded highly photoluminescent sulfur-zeolites with remarkably large Stokes shifts. An emission band at 650 nm for samples with low sulfur contents is observed when excited at 380 nm, which is fully consistent with S2– clusters as light-emitting centers. These orange emitting materials display external quantum efficiencies (EQEs) reaching 53% with peculiar high temperature photoluminescence stability up to 450 °C. For higher S/Cl molar ratios, a gradual conversion to near-infrared (NIR) light-emitting centers is observed with a maximum at 780 nm. This novel NIR luminescent species with EQEs of about 10% are attributed to polysulfide clusters (tentatively S42– species). Given the...

Highly photoluminescent two-dimensional imine-based covalent organic frameworks for chemical sensing.

The strong π-π interactions in the stacking layers of two-dimensional covalent organic frameworks (2D-COFs), together with rotationally labile imine linkages, make most of the solid state imine-linked COFs non-fluorescent due to fluorescence quenching processes. Here, we report the successful synthesis of highly photoluminescent imine-based 2D-COFs by integrating a non-planar building unit with a pyrene-based unit and transforming the COF into spherical, sub-micron particles. High photoluminescence quantum yields (PLQY) were achieved with COF sub-micron particles dispersed in organic solvents. The as-prepared COF sub-micron particles can be used as a chemical sensor for the detection of explosive chemicals, with high sensitivity and selectivity (up to ppm level).

Catalyst-Free Polyhydroboration of Dodecaborate Yields Highly Photoluminescent Ionic Polyarylated Clusters.

The incorporation of polyhedral boranes into novel photoluminescent materials is an area with increasing interest. While the neutral carboranes have been widely investigated for this purpose, the dodecaborate ion has received much less attention. Herein we report a significant expansion to the scope of substitution reactions for the dodecaborate ion, whereby this cluster was observed to react directly with a wide range of arenes in a step-wise and controlled manner. In the products of these reactions, the dodecaborate ion serves as a core upon which up to nine mono- or polycyclic aromatic hydrocarbon ligands are exohedrally bonded. Spectroscopic evidence suggests the presence of conjugation between the π systems of the aryl ligands and the dodecaborate core, resulting in materials which exhibit high solution-phase photoluminescence, as well as molar absorptivities and Stokes shifts that are significantly larger than those of the free arenes from which they were derived. We propose that this broad reactivity is a valuable synthetic tool for the incorporation of polyhedral boron into novel organic structures.

Femtosecond laser-assisted synthesis of highly photoluminescent carbon nanodots for Fe^3+ detection with high sensitivity and selectivity

Carbon nanodots (C-dots) were synthesized by femtosecond laser ablation of graphite powders in polyethylene glycol (PEG200N) solutions with different graphite concentrations. The photoluminescent quantum yield (PLQY) of the C-dots was effectively enhanced by decreasing the graphite concentration, and its value could reach 21%. Detailed work showed that the C-dots prepared with a low raw material concentration possessed high PLQY because they contained fewer trap defects in the carbogenic core and a larger quantity of surface functional groups on the surface. Taking advantage of their high photoluminescence properties, the C-dots were used as effective fluorescent nanosensor probes for sensitive and selective detection of Fe3+ ions.

Spectroscopic characteristics of carbon dots (C-dots) derived from carbon fibers and conversion to sulfur-bridged C-dots nanosheets.

We synthesized sub-10 nm carbon nanoparticles (CNPs) consistent with photoluminescent carbon dots (C-dots) from carbon fiber starting material. The production of different C-dots fractions was monitored over seven days. During the course of the reaction, one fraction of C-dots species with relatively high photoluminescence was short-lived, emerging during the first hour of reaction but disappearing after one day of reaction. Isolation of this species during the first hour of the reaction was crucial to obtaining higher-luminescent C-dots species. When the reaction proceeded for one week, the appearance of larger nanostructures was observed over time, with lateral dimensions approaching 200 nm. The experimental evidence suggests that these larger species are formed from small C-dot nanoparticles bridged together by sulfur-based moieties between the C-dot edge groups, as if the C-dots polymerized by cross-linking the edge groups through sulfur bridges. Their size can be tailored by controlling the reaction time. Our results highlight the variety of CNP products, from sub-10 nm C-dots to ~200 nm sulfur-containing carbon nanostructures, that can be produced over time during the oxidation reaction of the graphenic starting material. Our work provides a clear understanding of when to stop the oxidation reaction during the top-down production of C-dots to obtain highly photoluminescent species or a target average particle size.

Highly sensitive and selective detection of phosphate using novel highly photoluminescent water-soluble Mn-doped ZnTe/ZnSe quantum dots

Herein, the facile method with high selectivity for phosphate ion (Pi) sensing using novel Type-II core/shell Mn: ZnTe/ZnSe quantum dots (QDs) was reported. This was the first time that Mn: ZnTe/ZnSe QDs with highlighted optical properties were used for sensing. The water-soluble Mn: ZnTe/ZnSe QDs with a high quantum yield of 7% were synthesized by aqueous synthetic method. Compared with traditional ZnSe QDs or Mn: ZnSe QDs, the smaller effective band gap, longer wavelength and lower ionization potential (high valence band edge) for effective hole localization made Type-II core/shell Mn: ZnTe/ZnSe QDs to be stable and had high photoluminescence (PL). Only Mg2+ was found to be able to enhance Mn: ZnTe/ZnSe QDs PL selectively. The mechanism of fluorescence enhancement was attributed to the passivated surface nonradiative relaxation centers of Mn: ZnTe/ZnSe QDs. In the presence of Pi anion, the PL intensity got quenched due to the aggregation species of QDs via electrostatic attraction between Pi and Mg2+ on the surface of Mn: ZnTe/ZnSe QDs. Therefore, the quenching effect can be used to detect Pi selectively. The PL was observed to be linearly proportional to the Pi analyte concentration in the range from 0.67 to 50.0μmol/L, with a detection limit of 0.2μmol/L (S/N=3). The novel “on–off” fluorescence nanosensor for Pi detection was sensitive and convenient in the real analysis application. The reported analytical method of Mn: ZnTe/ZnSe QDs is highly sensitive and selective, which can corroborate the extension of its usages in chemo/ biosensing and bioimaging.

Preparation of highly luminescent hybrid gel incorporating NAC-capped CdTe quantum dots through sol–gel processing

Highly photoluminescent gel was prepared by embedding water soluble quantum dots (QDs) in an inorganic–organic hybrid gel matrix using a conventional sol–gel process. Aminopropyltrimethoxysilane and citric acid (CA) were found to be the best combination for the gel preparation. 13C-NMR and FT-IR studies indicated hydrogen bond formation between the amine group of APS and the carboxyl group of CA. IR-light radiation curing was comparable to thermal curing and reduced the gelation time to a considerable extent (71 %). The resulting composite formed a hybrid gel phosphor with excellent transparency by embedding CdTe QDs into the matrix and emitted light of various colors with high photoluminescence efficiency (40 %). The gel phosphor retained the PL properties after storage in air for one year. In addition, the strength of the hybrid phosphor was demonstrated by a coin-flipping test.

Highly photoluminescent low-temperature SiNx films in situ-deposited via SLAN ECR PECVD

Highly photoluminescent SiNx films were in situ-deposited at low temperatures using a slot-antenna electron-cyclotron-resonance (SLAN ECR) plasma. Spectroscopic ellipsometry, photoluminescence (PL) spectroscopy, high-resolution transmission electron microscopy (HRTEM), and UV–vis–NIR spectroscopy measurements were used to characterize the film. The SLAN ECR plasma, the ionization rate of which exceeds that of an RF plasma and a plasma density of approximately 1010–1011cm−3, is useful for high-quality film deposition at low temperatures. The deposited SiNx film displayed a high PL intensity, and as the SiH4/N2 ratio increased, the PL peak energy shifted from 2.8 to 1.7eV. These characteristics are useful for fabricating optoelectronic devices, such as LEDs and solar cells. As the silicon content in the SiNx film increased, the PL FWHM decreased. This effect deviated from the predictions based on the quantum confinement effect. The quantum dots did not properly form, as confirmed based on the HRTEM image. The linear relationship between the PL peak energy and the optical band gap energy suggested that bandtail recombination offered a more appropriate description of the PL mechanism than quantum confinement effects. Annealing and hyper-thermal neutral beam (HNB) treatment did not produce a shift in the PL peak, although the PL intensity decreased. These results also support the bandtail recombination model.

Green Synthesis of CuInS2/ZnS Nanocrystals with High Photoluminescence and Stability

Highly photoluminescent core/shell CuInS2/ZnS (CIS/ZnS) nanocrystals were synthesized. Zinc acetate and dodecanethiol in octadecene solvent were used for shell growth. The structure and composition of QDs were investigated with inductively coupled plasma‐optical emission spectroscopy, X‐ray photoelectron spectroscopy, and transmission electron microscopy. The crystal phase of CIS was tetragonal chalcopyrite. Based on X‐ray diffraction analysis, it has been concluded that the growth of the ZnS shell did not affect the phase structure of CuInS2 (CIS). Photoluminescence (PL) quantum yield (QY) of CIS increased to 80% after epitaxial growth of ZnS, and the PL emission wavelength can be feasibly tuned to be in the range of 560–710 nm by adjusting shell growth time. The superb photostability with high PL QY of CIS/ZnS nanocrystals is ascribed to the gradient of the chemical composition that has been formed between the core and the shell.

An ionic liquid promoted microwave-hydrothermal route towards highly photoluminescent carbon dots for sensitive and selective detection of iron(iii)

Carbon dots with a high photoluminescence efficiency of ∼22.58% are obtained by a facile microwave-hydrothermal treatment of rice straw with the presence of ionic liquid.

A facile microwave-hydrothermal approach towards highly photoluminescent carbon dots from goose feathers

Two-dimensional carbon dots with a high photoluminescence efficiency of ∼17.1% are obtained by the facile microwave-hydrothermal treatment of goose feathers.

Ultraslow recombination in AOT-capped TiO2 nanoparticles sensitized by protoporphyrin IX.

Aerosol OT (AOT) capped TiO2 nanoparticles have been prepared by a phase transfer mechanism. The TiO2 nanoparticles have a diameter of 5-10 nm, are highly crystalline (anatase) and show high photoluminescence. They are effectively sensitized by protoporphyrin IX (PPIX) and show high electron injection rates while the rate of back recombination is much slower than those reported previously. Thus the AOT capped TiO2 nanoparticles synthesized in this work are highly effective not only in promoting ultrafast electron injection from PPIX to TiO2 but more importantly they lead to extremely slow back recombination rates. The significance of this work is in the synthesis of highly photoluminescent TiO2 nanoparticles which can be easily sensitized by a porphyrin dye, whereby ultraslow recombination is observed.

Facile route to highly photoluminescent carbon nanodots for ion detection, pH sensors and bioimaging

Carbon nanodots (CDs) of uniform size were prepared simply by the hydrothermal decomposition of folic acid (FA) precursor at various reaction temperatures. The CDs formed via dehydration of FA at 260 °C contributed the strongest photoluminescence (PL) signal and the highest quantum yield at about 68%, without assistance of any passivation agent. The effects of preparation conditions on PL behavior of CDs have been investigated in detail, and the quantum yield of the CDs was found to be associated strongly with sample crystallinity. Moreover, because the obtained CDs also exhibited high luminescence stability, abundant surface functional groups and good biocompatibility, there are many promising applications in printing ink, ion detection, pH sensors and cell imaging.