Eco-Friendly Electrophoretic Deposition of Fluorescent Nanocomposite Films in an Aqueous Dispersion of Hydrophilized Core/Shell CuInS2/ZnS Quantum Dots for Optoelectronic Applications.

Low-toxic and efficient fluorescent core-shell CuInS2/ZnS (CIS/ZnS) quantum dots (QDs) are good candidates for optoelectronic device applications. They are synthesized in a hydrophobic environment, while large amounts of organic solvents used in the preparation of fluorescent films have significant problems on environmental load and human health. CIS/ZnS QDs hydrophilized by adsorbing 3-mercaptopropionic acid on their surfaces can be used in the aqueous film fabrication process. In this work, the aqueous electrophoretic deposition (EPD) of the hydrophilized QDs with silicone-modified acrylic resin nanoparticles was performed to fabricate fluorescent nanocomposite films. The hydrophilized QDs and resin nanoparticles were simultaneously dispersed in basic aqueous solutions due to electrostatic repulsion resulting from their negatively charged surfaces. Transparent films were obtained on a transparent conductive substrate at the anode side by the EPD. They showed yellow fluorescence of the QDs. The thickness increased with increasing the deposition time; however, hemispherical holes attributed to oxygen gas generated by water electrolysis were observed at the longer time. The electron microscopy revealed that the films were densely and homogeneously deposited. The QDs were dispersed around the resin nanoparticles without aggregation. The fluorescence (FL) quantum yield was 43%. The optical absorption peak and FL intensity of the QDs increased accompanied by the film growth. The nanocomposite film showed good heat resistance at 80-120 °C for 5 h; therefore, the prepared films have feasibility in white light-emitting diode (LED) applications. A lightening device structured with the obtained EPD film placed on a blue LED successfully emitted white light. In addition, the flexibility of the nanocomposite film was demonstrated. The aqueous EPD method would be one of the suitable methods for the industrial production of fluorescent QD films. This technique can be applied to other hydrophilic fluorescent QDs with charged surfaces. Realization of various fluorescent QD films would expand the application possibilities.

Enhanced and stabilized photoluminescence of perovskite cesium lead bromide nanocubes through ordered assemblies.

This work clarified the effects of self-assembly of perovskite cesium lead bromide (CsPbBr3) nanocubes (NCs) covered with didodecyldimethyl ammonium bromide (DDAB) on photoluminescence (PL) properties. Although the PL intensity of isolated NCs was weakened in the solid state even under inert conditions, the quantum yield of PL (PLQY) and the photostability of DDAB-covered NCs were drastically improved by the formation of two-dimensional (2D) ordered arrays on a substrate. The PLQY of the 2D arrays increased to ca. 60% by initial excitation illumination at 468 nm and was maintained for over 4000 h. The improved PL properties are attributable to the fixation of the surface ligand around the NCs in the specific ordered arrays.

Transparent Nanocomposites Comprising Ligand-Exchanged CuInS2/ZnS Quantum Dots and UV-Cured Resin for Wavelength Converters.

Quantum dots (QDs) dispersed in UV-curable resin are used for patterning in photolithography and inkjet printing. However, low affinity between the main component of UV-curable resins known as celloxide, an alicyclic diepoxy compound, and QD surface ligands with alkyl chains causes significant aggregation of QDs. In this study, the dispersibility of core/shell CuInS2/ZnS QDs with adsorbed 1-dodecanethiol and oleic acid in celloxide was improved using the ligand exchange method to prepare transparent fluorescent nanocomposites. Cyclohexyl 3-mercaptopropionate (MPACH) and 3-mercaptopropionic acid (MPA) were successfully adsorbed onto the QDs. MPACH-modified QDs (QD-MPACH) were well dispersed in the UV-curable resin, whereas MPA-modified QDs (QD-MPA) exhibited significant aggregation. Nanocomposite plates containing dispersed QDs were prepared by UV irradiation. The QD-MPACH nanocomposite plate was transparent, while the QD-MPA nanocomposite plate was turbid. The homogeneous dispersion of QD-MPACH was attributed to the similarity in the molecular structure between MPACH and celloxide. The photoluminescence (PL) peak of the QD-MPA nanocomposite occurred at a longer wavelength than that of the QD-MPACH nanocomposite. Furthermore, compared with the absolute photoluminescence quantum yield (PLQY) of the as-prepared QDs in toluene (55%), that of the QD-MPA nanocomposite was smaller (46%), and that of the QD-MPACH nanocomposite was higher (61%). An enhanced self-absorption effect was observed for the QD-MPA nanocomposite because of significant light scattering by the aggregates and concentration quenching, resulting in the PL redshift and decreased PLQY. Moreover, the PL intensity of the QD-MPACH nanocomposite was maintained at 98% of the initial value after continuous excitation-light irradiation for 5 h. The high PLQY and photostability of the QD-MPACH nanocomposite are beneficial in practical applications.

Improving the thermal resistance of fluorescent CsPb(Br,I)3 perovskite quantum dots by surface modification with perfluorodecanoic acid.

CsPb(Br,I)3 quantum dots (QDs) show application potential for optoelectronic devices. However, their thermal degradation is a significant problem. In this work, the effects of perfluorodecanoic acid (PFDA) modification on the photoluminescence (PL) and thermal resistance of CsPb(Br,I)3 QDs were evaluated. The PL intensity of oleic-acid-modified quantum dots (OA-QDs) in toluene decreased drastically upon heating at 100°C. The PL quantum yield of the QDs increased from 69.6% to 77.4% upon modification with PFDA. Furthermore, the PL intensity of the QDs modified with PFDA (PFDA-QDs) increased to 140.6% upon heating, because of the reduction of surface defects upon adsorption of PFDA and its optimized adsorption state. A solid-film PFDA-QDs sample heated at 80°C for 4 h showed temporary PL enhancements for the OA-QDs and PFDA-QDs films to 445% and 557% of their initial values, respectively, upon heating for 0.25 h. This was attributed to the optimized adsorption states of the surface ligands. PFDA-QDs film maintained 354% after 4 h of heating, whereas that of OA-QDs film was 104%. Thus, PFDA modification enhances PL intensity and suppresses PL degradation under heating, which is important for wavelength converters for optoelectronic device applications.

Glycothermally Synthesized Carbon Dots with Narrow-Bandwidth and Color-Tunable Solvatochromic Fluorescence for Wide-Color-Gamut Displays.

Fluorescent carbon dots (CDs) represent a promising eco-friendly next-generation phosphor. However, most CDs exhibit broad photoluminescence (PL) spectra [full width at half-maximum (fwhm) over 60 nm]; few works on CDs with sharp PL spectra (fwhm less than 40 nm) have been reported. In addition, their syntheses and color tuning require harsh conditions of high temperatures, long reaction times, and high pressures with catalysts. Here, we successfully prepared narrow-bandwidth emissive CDs (fwhm of 27-40 nm) from phloroglucinol in a glycol solvent of 1,2-pentanediol at temperatures as low as 180 °C for a reaction duration of as short as 6 h under ambient conditions without any catalysts via an open reaction system in which dehydration and condensation reactions among phloroglucinol molecules were enhanced. We shifted the emission peak from 463 to 511 nm by selecting seven kinds of solvents with different polarities, that is, emission colors could be tuned from blue to green by taking advantage of fluorescence solvatochromism. The CD-dispersed polymer films showed a similar solvatochromic behavior and sharp PL spectra, verifying the feasibility of applying the CDs to displays with a wide color gamut.

Effective Stabilization of Perovskite Cesium Lead Bromide Nanocrystals through Facile Surface Modification by Perfluorocarbon Acid.

CsPbX3 (X = Cl, Br, I) perovskite nanocrystals (NCs) have attracted much attention as promising materials for next-generation optoelectronic applications. However, improvement of their low stabilities against heating and humidity is needed for practical use. In this work, we focused on perfluorodecanoic acid (PFDA) as a surface ligand and investigated the thermal and chemical stabilities of the photoluminescence (PL) properties of CsPbBr3 NCs. Oleic acid (OA) adsorbed on the NCs was exchanged for decanoic acid (DA) and PFDA. OA-modified and DA-modified NCs exhibited drastic fluorescence quenching to 12.9 and 21.1% of their initial PL intensities, respectively, after heating at 100 °C for 4 h. In contrast, the PFDA-modified NCs maintained 92.1% of their PL intensity after the same heating. Furthermore, the polar solvent resistance was also improved by PFDA modification. These improvements can be attributed to the strong adsorptivity and high chemical stability of the PFDA ligand.

Surface modification strategy for fluorescence solvatochromism of carbon dots prepared from p-phenylenediamine.

The fluorescence solvatochromism of p-phenylenediamine-derived carbon dots (CDs) was modulated through surface modification with decanoic acid or perfluorodecanoic acid. This is attributed to the adjustment of the dipole interaction between solvent molecules and the CD surface in terms of steric hindrance of a surface modifier and polarization of the modified CD surface.

Fluorescence Solvatochromism of Carbon Dot Dispersions Prepared from Phenylenediamine and Optimization of Red Emission.

Fluorescent carbon dots (CDs) are of interest as a promising alternative to quantum dots, partly because they do not include heavy metals. However, most CDs exhibit blue or green emission, while red-emitting CDs are required for a variety of applications. In the present work, CDs were synthesized by refluxing three phenylenediamine (PD) isomers with amino groups at different positions (o-PD, m-PD, and p-PD) in diphenyl ether at 250 °C for 4 h. Upon dispersing the resulting CDs in eight solvents with different polarities, emission colors ranging from green to red were observed. Among these CDs, p-PD-derived CDs exhibited both the longest emission wavelength range, from 538 to 635 nm, and the highest absolute red photoluminescence quantum yield (PLQY) of 15%. Herein the results are discussed based on a comparison of the polymerization processes of o-PD, m-PD, and p-PD. This work demonstrated that the optimum reaction time was 2 h, which yields a p-PD-derived CD dispersion in methanol with red emission and an absolute PLQY as high as 18%. Additionally, the use of 1-decanol and deuterated methanol in place of methanol improved the maximum absolute PLQY to 25% and 36%, respectively. These improved values are attributed to reduced concentration quenching by suppression of π-π stacking interactions and inhibition of the nonradiative relaxation process through the vibration of OH groups, respectively.

Green Photoluminescence of Perovskite CsPb(Br1-x I x )3 Nanocrystals for Wide Color Gamut Displays.

All-inorganic mixed-halide CsPb(Br1-x I x )3 perovskite nanocrystals (NCs) are excellent candidates for green-emitting phosphors in wide color gamut displays; however, a detailed investigation of their photoluminescence (PL) properties based on the halide composition has been missing. In this work, we report a fundamental investigation of the changes in the PL properties of CsPb(Br1-x I x )3 NCs. The PL color of the NCs, which were prepared by a hot-injection method, changed from green to red with increasing iodide composition (x). Almost ideal green emission close to the chromaticity coordinates of the green vertex of the BT.2020 standard was achieved by appropriately substituting iodide ions for bromide ions in monohalide CsPbBr3 NCs. However, the PL peak width of the mix-halide NCs at x ∼ 0.5 was 0.127 eV, which was broader than the 0.105 eV peak width of the monohalide CsPbBr3 NCs. This phenomenon should be due to the compositional inhomogeneity among the individual CsPb(Br1-x I x )3 NCs. On the other hand, the PL quantum yield (PLQY) for the monohalide CsPbBr3 NCs decreased from 70 to 25% as x increased to 0.5. This result may be attributed to lattice distortion by the difference in the ionic radii of bromide and iodide. Improvements in the compositional inhomogeneity and lattice distortion would enhance the color purity of the green emission and the PLQY, respectively, of the CsPb(Br1-x I x )3 NCs.

Electrophoretically Deposited Y2O3:Bi3+,Eu3+ Nanosheet Films with High Transparency for Near-Ultraviolet to Red Light Conversion.

Fluorescent films were fabricated by depositing Y2O3:Bi3+,Eu3+ nanosheets, which emit red light under near-UV irradiation. The Y2O3:Bi3+,Eu3+ nanosheets were obtained by calcining hydroxide precursor nanosheets synthesized through a hydrothermal method. An aqueous dispersion of positively charged Y2O3:Bi3+,Eu3+ nanosheets with polyethyleneimine adsorbed to the surface was prepared for their deposition. Fluorescent nanosheets were electrophoretically deposited on a transparent conductive substrate under a constant voltage. The obtained nanosheet films were dense and uniform and showed excellent photostability against the excitation light. Growth of the nanosheet film caused a decrease in transmittance and an increase in the photoluminescence intensity. The former effect was attributed to light scattering from inner voids and the rough surface of the film. A polyvinylpyrrolidone (PVP) coating on the film improved the transmittance to be greater than 70% over the visible region. These effects were attributed to antireflection effects at the film surface owing to the low refractive index of PVP. Furthermore, suppression of light scattering by coating the rough surface with a smooth PVP film and filling of voids in the nanosheet film with PVP also improved the transmittance.

Photoluminescence color stability of green-emitting InP/ZnS core/shell quantum dots embedded in silica prepared via hydrophobic routes.

In this work, green-emitting InP/ZnS quantum dots (QDs) modified with 1-dodecanethiol were embedded into silica by two methods to improve their photostability while maintaining a high photoluminescence quantum yield (PLQY) and a color coordinate. A monolithic QD-silica composite prepared by a non-aqueous route with tetraethyl orthosilicate and lactic acid featured low transparency, a loss of the color purity of green, and a PLQY of 1.6%, which was considerably lower than that of the original QDs (67%). The decrease of the PLQY was attributed to QD aggregation in the sol-gel process and degradation of the QDs by the acid. The alternative method involved stirring a toluene dispersion of the QDs with tetramethyl orthosilicate (TMOS) for 20 h or 7 days. The PLQY of the TMOS-modified InP/ZnS QDs (20 h) was 62%, which was only slightly lower than that of the original QDs. The PLQY decreased to 52% when the duration of aging was prolonged to 7 days. This decrease was attributed to desorption of surface modifiers from the QD surface and oxidative degradation by oxygen dissolved in toluene. Herein, the color coordinate was maintained stably. Photostability was evaluated by continuous irradiation of the samples by a blue light emitting diode. The decrease of photoluminescence (PL) intensity was suppressed by the silica encapsulation. In particular, the PL intensity of the TMOS-modified InP/ZnS QD sample (7 d) maintained 99% of its initial intensity. Silica encapsulation of InP/ZnS QDs prevented contact of the QDs with oxygen in the air, resulting in improved photostability.

Composites of Eu(3+)-doped calcium apatite nanoparticles and silica particles: comparative study of two preparation methods.

We synthesized composites of Eu(3+)-doped calcium apatite (CaAp:Eu(3+)) nanoparticles and silica particles via two methods: (i) in situ synthesis of CaAp:Eu(3+) in the presence of silica particles and (ii) electrostatic adsorption of CaAp:Eu(3+) nanoparticles on silica particle surfaces. In both methods, submicrometer spherical silica particles were covered with CaAp:Eu(3+) nanoparticles without forming any impurity phases, as confirmed by X-ray diffractometry, Fourier-transform infrared spectroscopy, and scanning electron microscopy. In method i, part of the silica surface acted as a nucleation site for apatite crystals and silica particles were inhomogeneously covered with CaAp:Eu(3+) nanoparticles. In method ii, positively charged CaAp:Eu(3+) nanoparticles were homogeneously adsorbed on the negatively charged silica surface through electrostatic interactions. The bonds between the silica surface and CaAp:Eu(3+) nanoparticles are strong enough not to break under ultrasonic irradiation, irrespective of the synthetic method used. The composite particles showed red photoluminescence corresponding to 4f → 4f transitions of Eu(3+) under near-UV irradiation. Although the absorption coefficient of the forbidden 4f → 4f transitions of Eu(3+) was small, the red emission was detectable with a commercial fluorescence microscope because the CaAp:Eu(3+) nanoparticles accumulated on the silica particle surfaces.

Electrophoretic deposition and characterization of transparent nanocomposite films of YVO4:Bi3+,Eu3+ nanophosphor and silicone-modified acrylic resin.

We fabricated nanocomposite films from an aqueous suspension of red-emitting YVO4:Bi(3+),Eu(3+) nanoparticles (hydrodynamic size: 22 ± 6 nm) and silicone-modified acrylic resin nanoparticles of (60 ± 15 nm) by electrophoretic deposition under application of a constant voltage. The nanocomposite films were formed from these negatively charged nanoparticles on ITO-coated glass substrates on the anodic side at the volume ratio of nanophosphor:resin ∼ 40:60. According to transmission electron microscopy observations, the YVO4:Bi(3+),Eu(3+) nanoparticles are well-dispersed around the resin nanoparticles. The fabricated films are transparent to the naked eye under white light because both nanoparticles show no absorption and low light scattering in the visible region. A silicone-modified acrylic resin film without the nanophosphor exhibits no absorption in the UV region (>300.0 nm). However, the fabricated nanocomposite films show near-UV absorption owing to the interband transition between the valence band and the conduction band of the YVO4:Bi(3+),Eu(3+) nanoparticles. A sharp emission peak corresponding to the (5)D0 → (7)F2 transition of Eu(3+) is observed at 619.5 nm, under 365.0 nm excitation, for each nanocomposite film. The photoluminescence intensity at 619.5 nm under 365.0 nm excitation is proportional to 1-10(-OD) (OD: optical density at 365.0 nm) for film thicknesses ≤6 µm. This is attributed to the low light scattering from both nanoparticles in the nanocomposite film. Conversely, the observed photoluminescence intensity for film thicknesses >6 µm is higher than the value expected from the proportional relationship. This suggests that the excitation of the nanophosphors efficiently occurs due to multiple scattering of excitation light.

Tagging of avidin immobilized beads with biotinylated YAG:Ce3+ nanocrystal phosphor.

YAG:Ce3+ nanoparticles 9.5+/-1.2 nm in diameter have been synthesized from aluminium isopropoxide and acetates of yttrium and cerium in 1,4-butanediol (1,4-BD) by autoclave treatment at 300 degrees C for 2 h. After replacing 1,4-BD by ultrapure water, NH2 groups were introduced on the surface of YAG:Ce3+ nanoparticles by addition of 3-aminopropyltrimethoxysilane then biotinylation with sulfo-NHS-LC-biotin. We demonstrated that avidin immobilized beads are tagged by biotinylated YAG:Ce3+ nanoparticles by the selective avidin-biotin interaction, furnishing a green fluorescent image on excitation with blue light. This result indicates that YAG:Ce3+ nanoparticle phosphors have much potential in biological applications.

Photoluminescence enhancement of PEG-modified YAG:Ce3+ nanocrystal phosphor prepared by glycothermal method.

Y3Al5O12:Ce3+ (YAG:Ce3+) nanocrystals were synthesized in 1,4-butylene glycol (BG) with and without poly(ethylene glycol) (PEG) by the glycothermal method. The internal quantum efficiency of the photoluminescence (PL) corresponding to the 5d --> 4f transition of Ce3+ in the YAG:Ce3+ nanocrystal increased from 21.3 to 37.9% by addition of PEG, while no appreciable change in the primary particle size, the crystallite size, and the lattice distortion was recognized by transmission electron microscopy and X-ray diffractometry. The thermogravimetry-differential thermal analysis, Fourier transform infrared absorption spectroscopy and 1H --> 13C cross-polarization magic angle spinning nuclear magnetic resonance (CP-MAS NMR) confirmed the preferential coordination of PEG to the YAG:Ce3+ nanocrystal. 27Al single-pulse excitation MAS NMR reveals that the ratio of the 4-fold coordination site to the 6-fold coordination site increased from 0.53 to 0.72 by addition of PEG. We conclude that the surface modification of the YAG:Ce3+ nanocrystal by PEG induces the surface passivation, the prevention of the oxidation of Ce3+ to Ce4+, the promotion of the incorporation of Ce3+ into YAG and the local structural rearrangement, resulting in the PL enhancement.