Correction: Water-dispersible donor-acceptor-donor π-conjugated bolaamphiphiles enabling a humidity-responsive luminescence color change.

Correction for 'Water-dispersible donor-acceptor-donor π-conjugated bolaamphiphiles enabling a humidity-responsive luminescence color change' by Tomoya Enjou et al., Chem. Commun., 2024, https://doi.org/10.1039/d3cc05749f.

Spectrally narrow band-edge photoluminescence from AgInS2-based core/shell quantum dots for electroluminescence applications.

This study presents a facile synthesis of cadmium-free ternary and quaternary quantum dots (QDs) and their application to light-emitting diode (LED) devices. AgInS2 ternary QDs, developed as a substitute for cadmium chalcogenide QDs, exhibited spectrally broad photoluminescence due to intrinsic defect levels. Our group has successfully achieved narrow band-edge PL by a coating with gallium sulfide shell. Subsequently, an intrinsic difficulty in the synthesis of multinary compound QDs, which often results in unnecessary byproducts, was surmounted by a new approach involving the nucleation of silver sulfide followed by material conversion to the intended composition (silver indium gallium sulfide). By fine-tuning this reaction and bringing the starting material closer to stoichiometric compositional ratios, atom economy was further improved. These QDs have been tested in LED applications, but the standard device encountered a significant defective emission that would have been eliminated by the gallium sulfide shells. This problem is addressed by introducing gallium oxide as a new electron transport layer.

One-pot synthesis of Ag-In-Ga-S nanocrystals embedded in a Ga2O3 matrix and enhancement of band-edge emission by Na+ doping.

I-III-VI-based semiconductor quantum dots (QDs) have been intensively explored because of their unique controllable optoelectronic properties. Here we report one-pot synthesis of Na-doped Ag-In-Ga-S (AIGS) QDs incorporated in a Ga2O3 matrix. The obtained QDs showed a sharp band-edge photoluminescence peak at 557 nm without a broad-defect site emission. The PL quantum yield (QY) of such QDs was 58%, being much higher than that of AIGS QDs without Na+ doping, 29%. The obtained Na-doped AIGS/Ga2O3 composite particles were used as an emitting layer of green QD light-emitted diodes. A sharp electroluminescence (EL) peak was observed at 563 nm, being similar to that in the PL spectrum of the QDs used. The external quantum efficiency of the device was 0.6%.

Development of Cu-In-Ga-S quantum dots with a narrow emission peak for red electroluminescence.

Narrowing the emission peak width and adjusting the peak position play a key role in the chromaticity and color accuracy of display devices with the use of quantum dot light-emitting diodes (QD-LEDs). In this study, we developed multinary Cu-In-Ga-S (CIGS) QDs showing a narrow photoluminescence (PL) peak by controlling the Cu fraction, i.e., Cu/(In+Ga), and the ratio of In to Ga composing the QDs. The energy gap of CIGS QDs was enlarged from 1.74 to 2.77 eV with a decrease in the In/(In+Ga) ratio from 1.0 to 0. The PL intensity was remarkably dependent on the Cu fraction, and the PL peak width was dependent on the In/(In+Ga) ratio. The sharpest PL peak at 668 nm with a full width at half maximum (fwhm) of 0.23 eV was obtained for CIGS QDs prepared with ratios of Cu/(In+Ga) = 0.3 and In/(In+Ga) = 0.7, being much narrower than those previously reported with CIGS QDs, fwhm of >0.4 eV. The PL quantum yield of CIGS QDs, 8.3%, was increased to 27% and 46% without a PL peak broadening by surface coating with GaSx and Ga-Zn-S shells, respectively. Considering a large Stokes shift of >0.5 eV and the predominant PL decay component of ∼200-400 ns, the narrow PL peak was assignable to the emission from intragap states. QD-LEDs fabricated with CIGS QDs surface-coated with GaSx shells showed a red color with a narrow emission peak at 688 nm with a fwhm of 0.24 eV.

Quantum-Dot Light-Emitting Diodes Exhibiting Narrow-Spectrum Green Electroluminescence by Using Ag-In-Ga-S/GaSx Quantum Dots.

Quantum dots (QDs), which have high color purity, are expected to be applied as emitting materials to wide-color-gamut displays. To enable their use as an alternative to Cd-based QDs, it is necessary to improve the properties of QDs composed of low-toxicity materials. Although multielement QDs such as Ag-In-Ga-S are prone to spectrally broad emission from defect sites, a core/shell structure covered with a GaSx shell is expected to enable sharp emission from band-edge transitions. Here, QD light-emitting diodes (QD-LEDs) embedded with Ag-In-Ga-S/GaSx core/shell QDs (AIGS QDs) were fabricated, and their electroluminescence (EL) was observed. The EL spectra from the AIGS QD-LEDs were found to contain a large defect-related emission component not observed in the photoluminescence (PL) spectra of the AIGS QD films. This defect-related emission was caused by electrons injected into defect sites in the QDs. Therefore, the AIGS QDs and the electron injection layer (EIL) of ZnMgO were treated with Ga compounds such as gallium chloride (GaCl3) and gallium tris(N,N'-diethyldithiocarbamate) (Ga(DDTC)3) to improve the luminescence properties of the QD-LEDs. The added Ga compounds effectively compensated for defect sites on the surface of the QDs and suppressed direct electron injection from the EIL into defect sites. As a result, the defect-related emission components in the EL were successfully suppressed, and the EL exhibited a color purity comparable to the PL of the AIGS QD films. The QD-LEDs exhibited EL spectra with a full width at half-maximum of 33 nm, which is extremely sharp for a low-toxicity QD, and the chromaticity coordinates (0.260, 0.695) for green EL were achieved.

Surface ligand chemistry on quaternary Ag(In x Ga1-x )S2 semiconductor quantum dots for improving photoluminescence properties.

Ternary and quaternary semiconductor quantum dots (QDs) are candidates for cadmium-free alternatives. Among these, semiconductors containing elements from groups 11, 13, and 16 (i.e., I-III-VI2) are attracting increasing attention since they are direct semiconductors whose bandgap energies in the bulk state are tunable between visible and near infrared. The quaternary system of alloys consisting of silver indium sulfide (AgInS2; bandgap energy: E g = 1.8 eV) and silver gallium sulfide (AgGaS2; E g = 2.4 eV) (i.e., Ag[In x Ga1-x ]S2 (AIGS)) enables bandgap tuning over a wide range of visible light. However, the photoluminescence (PL) quantum yield (10-20%) of AIGS QDs is significantly lower than that of AgInS2 (60-70%). The present study investigates how to improve the PL quantum yield of AIGS QDs via surface ligand engineering. Firstly, the use of a mixture of oleic acid and oleylamine, instead of only oleylamine, as the solvent for the QD synthesis was attempted, and a threefold improvement of the PL quantum yield was achieved. Subsequently, a post-synthetic ligand exchange was performed. Although the addition of alkylphosphine, which is known as an L-type ligand, improved the PL efficiency only by 20%, the use of metal halides, which are categorized as Z-type ligands, demonstrated a twofold to threefold improvement of the PL quantum yield, with the highest value reaching 73.4%. The same procedure was applied to the band-edge emitting core/shell-like QDs that were synthesized in one batch based on our previous findings. While the as-prepared core/shell-like QDs exhibited a PL quantum yield of only 9%, the PL quantum yield increased to 49.5% after treatment with metal halides.

Synthesis of multicolor-emitting nitrogen-sulfur co-doped carbon dots and their photochemical studies for sensing applications.

Photoluminescent carbon dots (CDs) possess several advantages, which include high stability and a non-toxicity that are essential in different applications such as catalysis, drug delivery, and sensors. The presence of heteroatoms modifies their physicochemical characteristics. In this work, a combination of CDs is manufactured utilizing a solvothermal technique using citric acid and thiourea. After separating each section using column chromatography, green and yellow CDs with average diameters of 8.3 and 7.0 nm, respectively, are generated. Next, optical and structural characterizations indicated that the variation in the emission color was caused by differences in surface functional groups rather than particle size. The photoelectrochemical properties are explored by including quinone derivatives and metal ions, which are quenchers for the CDs. The photoluminescence quenching results showed the presence of anionic functional groups on the surface of the CDs. Furthermore, these functional groups interacted strongly with particular types of metal ions, indicating that they may be employed as metal ion sensors.

Luminescent Quaternary Ag(InxGa1-x)S2/GaSy Core/Shell Quantum Dots Prepared Using Dithiocarbamate Compounds and Photoluminescence Recovery via Post Treatment.

Cadmium-free quantum dots (QDs) consisting of silver-indium-gallium-sulfide (AIGS) quaternary semiconductors were successfully synthesized using a metal-dithiocarbamate complex with sufficiently high reactivity to produce metal sulfides. The introduction of a gallium diethyldithiocarbamate precursor decreased the reaction temperature to produce active intermediates, which were subsequently converted into AIGS QDs at 150 °C with silver and indium acetates. Because of the low reaction temperature, AIGS QDs with a tetragonal crystal phase were produced selectively, which favorably generated band-edge emission whose full width at half-maximum is smaller than 40 nm after they were coated with gallium sulfide (GaSy) shells. The compositional indium/gallium ratio was varied by changing the mixing ratio of the precursors used for the synthesis of the AIGS core, and the band-edge photoluminescence (PL) generated from the AIGS/GaSy core/shell QDs was blue-shifted with an increase in the gallium content in the core. Consequently, a pure green emission centered at 518 nm was obtained with a PL quantum yield as high as 68%.

Core Nanoparticle Engineering for Narrower and More Intense Band-Edge Emission from AgInS2/GaSx Core/Shell Quantum Dots.

Highly luminescent silver indium sulfide (AgInS2) nanoparticles were synthesized by dropwise injection of a sulfur precursor solution into a cationic metal precursor solution. The two-step reaction including the formation of silver sulfide (Ag2S) nanoparticles as an intermediate and their conversion to AgInS2 nanoparticles, occurred during the dropwise injection. The crystal structure of the AgInS2 nanoparticles differed according to the temperature of the metal precursor solution. Specifically, the tetragonal crystal phase was obtained at 140 °C, and the orthorhombic crystal phase was obtained at 180 °C. Furthermore, when the AgInS2 nanoparticles were coated with a gallium sulfide (GaSx) shell, the nanoparticles with both crystal phases emitted a spectrally narrow luminescence, which originated from the band-edge transition of AgInS2. Tetragonal AgInS2 exhibited narrower band-edge emission (full width at half maximum, FWHM = 32.2 nm) and higher photoluminescence (PL) quantum yield (QY) (49.2%) than those of the orthorhombic AgInS2 nanoparticles (FWHM = 37.8 nm, QY = 33.3%). Additional surface passivation by alkylphosphine resulted in higher PL QY (72.3%) with a narrow spectral shape.

Wavelength-Tunable Band-Edge Photoluminescence of Nonstoichiometric Ag-In-S Nanoparticles via Ga3+ Doping.

The nonstoichiometry of I-III-VI semiconductor nanoparticles, especially the ratio of group I to group III elements, has been utilized to control their physicochemical properties. We report the solution-phase synthesis of nonstoichiometric Ag-In-S and Ag-In-Ga-S nanoparticles and results of the investigation of their photoluminescence (PL) properties in relation to their chemical compositions. While stoichiometric AgInS2 nanoparticles simply exhibited only a broad PL band originating from defect sites in the particles, a narrow band edge PL peak newly appeared with a decrease in the Ag fraction in the nonstoichiometric Ag-In-S nanoparticles. The relative PL intensity of this band edge emission with respect to the defect-site emission was optimal at a Ag/(Ag + In) value of ca. 0.4. The peak wavelength of the band edge emission was tunable from 610 to 500 nm by increased doping with Ga3+ into Ag-In-S nanoparticles due to an increase of the energy gap. Furthermore, surface coating of Ga3+-doped Ag-In-S nanoparticles, that is, Ag-In-Ga-S nanoparticles, with a GaS x shell drastically and selectively suppressed the broad defect-site PL peak and, at the same time, led to an increase in the PL quantum yield (QY) of the band edge emission peak. The optimal PL QY was 28% for Ag-In-Ga-S@GaS x core-shell particles, with green band-edge emission at 530 nm and a full width at half-maximum of 181 meV (41 nm). The observed wavelength tunability of the band-edge PL peak will facilitate possible use of these toxic-element-free I-III-VI-based nanoparticles in a wide area of applications.

Controlling Shape Anisotropy of ZnS-AgInS2 Solid Solution Nanoparticles for Improving Photocatalytic Activity.

Independently controlling the shape anisotropy and chemical composition of multinary semiconductor particles is important for preparing highly efficient photocatalysts. In this study, we prepared ZnS-AgInS2 solid solution ((AgIn)xZn2(1-x)S2, ZAIS) nanoparticles with well-controlled anisotropic shapes, rod and rice shapes, by reacting corresponding metal acetates with a mixture of sulfur compounds with different reactivities, elemental sulfur, and 1,3-dibutylthiourea, via a two-step heating-up process. The chemical composition predominantly determined the energy gap of ZAIS particles: the fraction of Zn2+ in rod-shaped particles was tuned by the ratio of metal precursors used in the nanocrystal formation, while postpreparative Zn2+ doping was necessary to increase the Zn2+ fraction in the rice-shaped particles. The photocatalytic H2 evolution rate with irradiation to ZAIS particles dispersed in an aqueous solution was significantly dependent on the chemical composition in the case of using photocatalyst particles with a constant morphology. In contrast, photocatalytic activity at the optimum ZAIS composition, x of 0.35-0.45, increased with particle morphology in the order of rice (size: ca. 9 × ca. 16 nm) < sphere (diameter: ca. 5.5 nm) < rod (size: 4.6 × 27 nm). The highest apparent quantum yield for photocatalytic H2 evolution was 5.9% for rod-shaped ZAIS particles, being about two times larger than that obtained with spherical particles.

Photocatalytic Properties of TiO2 Composites Immobilized with Gold Nanoparticle Assemblies Using the Streptavidin-Biotin Interaction.

A method using biomolecules to precisely fabricate the morphology of metal nanoparticles immobilized on the surface of a semiconductor using biomolecules is described. A biotin moiety (Biot) is introduced onto the surface of a gold nanoparticle (AuNP) by covalent coupling with α-lipoic acid to assemble AuNPs in the presence of streptavidin (STV). The assembly of Biot-AuNP/STV is immobilized on the surface of TiO2 chemically modified with 1-(3-aminopropyl)silatrane (APS) to provide a positively charged surface. The Au content immobilized on the surface of TiO2 is clearly increased to 9.5 wt % (Au) as a result of the STV-biotin interaction and the electrostatic interaction between negatively charged Biot-AuNPs and the positively charged surface of APS/TiO2. Transmission electron microscopy (TEM) analysis reveals that the composite has an ordered surface geometry in which Biot-AuNPs are spread over the composite surface in two dimensions. The photocatalytic activity toward decomposition of methyl orange dye promoted by this composite is 55%, which is higher than that of the other composites. The Biot-AuNP/STV@APS/TiO2 composite efficiently reduces O2 molecules at Eonset = -0.23 V vs Ag|AgCl, which is more positive than that of other composites (Eonset = -0.40 to -0.32 V). The result suggests that an increased number of AuNPs immobilized in close contact with the TiO2 surface facilitates photoinduced charge transfer. This strategy, which takes advantage of the specific interactions provided by biomolecules and the chemical modification on the surface, has remarkable potential for efficient fabrication of metal nanoparticles on the surface of the semiconductor, which accelerates the reduction of oxygen molecules.

Mannose-displaying fluorescent framboidal nanoparticles containing phenylboronic acid groups as a potential drug carrier for macrophage targeting.

Functional polymeric nanoparticles have been used for various applications in the biomaterials field. Recently, we reported phenylboronic acid-containing nanoparticles (PBA NPs) having an unique framboidal morphology, prepared in a single-step by the aqueous dispersion polymerization of N-acryloyl-3-aminophenylboronic acid (PBAAM) in the presence of poly(ethylene glycol) acrylamide (PEGAM) as a polymerizable dispersant and N,N'-methylenebisacrylamide (MBAM) as a crosslinker. In this study, we prepared mannosylated and fluorescent PBA NPs that could be used for different applications such as drug delivery and bioimaging. Fluorescent PBA NPs were synthesized by including the fluorescent Nile Blue acrylamide monomer in the reaction mixture during the dispersion polymerization of PBAAM. By using a carboxyl group-bearing PEGAM dispersant, carboxyl group-bearing PBA NPs were prepared that were modified with mannosamine to yield mannosylated PBA NPs. Cellular uptake studies showed that the mannosylated PBA NPs were selectively taken up by murine RAW264.7 macrophages. These results show that PBA NPs allow for flexible modification with various functionalities and could therefore be a potential platform for targeted delivery of drugs to macrophages.

Atomic resolution imaging of gold nanoparticle generation and growth in ionic liquids.

Recent advances in in situ transmission electron microscopy (TEM) techniques have provided unprecedented knowledge of chemical reactions from a microscopic viewpoint. To introduce volatile liquids, in which chemical reactions take place, use of sophisticated tailor-made fluid cells is a usual method. Herein, a very simple method is presented, which takes advantage of nonvolatile ionic liquids without any fluid cell. This method is successfully employed to investigate the essential steps in the generation of gold nanoparticles as well as the growth kinetics of individual particles. The ionic liquids that we select do not exhibit any anomalous effects on the reaction process as compared with recent in situ TEM studies using conventional solvents. Thus, obtained TEM movies largely support not only classical theory of nanoparticle generation but also some nonconventional phenomena that have been expected recently by some researchers. More noteworthy is the clear observation of lattice fringes by high-resolution TEM even in the ionic liquid media, providing intriguing information correlating coalescence with crystal states. The relaxation of nanoparticle shape and crystal structure after the coalescence is investigated in detail. The effect of crystal orientation upon coalescence is also analyzed and discussed.

Cadmium-free sugar-chain-immobilized fluorescent nanoparticles containing low-toxicity ZnS-AgInS2 cores for probing lectin and cells.

Sugar chains play a significant role in various biological processes through sugar chain-protein and sugar chain-sugar chain interactions. To date, various tools for analyzing sugar chains biofunctions have been developed. Fluorescent nanoparticles (FNPs) functionalized with carbohydrate, such as quantum dots (QDs), are an attractive imaging tool for analyzing carbohydrate biofunctions in vitro and in vivo. Most FNPs, however, consist of highly toxic elements such as cadmium, tellurium, selenium, and so on, causing problems in long-term bioimaging because of their cytotoxicity. In this study, we developed cadmium-free sugar-chain-immobilized fluorescent nanoparticles (SFNPs) using ZnS-AgInS2 (ZAIS) solid solution nanoparticles (NPs) of low or negligible toxicity as core components, and investigated their bioavailability and cytotoxicity. SFNPs were prepared by mixing our originally developed sugar-chain-ligand conjugates with ZAIS/ZnS core/shell NPs. In binding experiments with lectin, the obtained ZAIS/ZnS SFNPs interacted with an appropriate lectin to give specific aggregates, and their binding interaction was visually and/or spectroscopically detected. In addition, these SFNPs were successfully utilized for cytometry analysis and cellular imaging in which the cell was found to possess different sugar-binding properties. The results of the cytotoxicity assay indicated that SFNPs containing ZAIS/ZnS have much lower toxicity than those containing cadmium. These data strongly suggest that our designed SFNPs can be widely utilized in various biosensing applications involved in carbohydrates.

Photocurrent generation from hierarchical zinc-substituted hemoprotein assemblies immobilized on a gold electrode.

All connected: a protein-immobilized electrode comprising hierarchical assemblies of photoactive cytochrome b(562) reconstituted with zinc protoporphyrin IX exhibits remarkably enhanced photocurrent generation relative to an electrode bearing a single zinc-substituted hemoprotein layer. The protein oligomers, which bear a covalently linked protoporphyrin group, assemble by a supramolecular heme/heme pocket interaction.