Enhancement mechanism of quantum yield in core/shell/shell quantum dots of ZnS-AgIn5S8/ZnIn2S4/ZnS.

To achieve a high quantum yield (QY) of nanomaterials suitable for optical applications, we improved the optical properties of AgIn5S8 (AIS) quantum dots (QDs) by employing an alloyed-core/inner-shell/outer-shell (ZAIS/ZIS/ZnS) structure. We also investigated the mechanism of optical transitions to clarify the improvement of QYs. In AIS, the low-energy absorption near the band edge region is attributed to the weakly allowed band gap transition, which gains oscillator strength through state intermixing and electron-phonon coupling. The main photoluminescence is also ascribed to the weakly allowed band gap transition with characteristics of self-trapped excitonic emission. With alloying/shelling processes, the weakly allowed transition is enhanced by the evolution of the electronic structures in the alloyed core, which improves the band gap emission. In shelled structures, the nonradiative process is reduced by the reconstructed lattice and passivated surface, ultimately leading to a high QY of 85% in ZAIS/ZIS/ZnS. These findings provide new insights into the optical transitions of AIS because they challenge previous conclusions. In addition, our work elucidates the mechanism behind the enhancement of QY accomplished through alloying/shelling processes, providing strategies to optimize nontoxic QDs for various applications using a green chemistry approach.

Distinctive optical transitions of tunable multicolor carbon dots.

Three types of carbon dots (CDs) are synthesized from isomers of phenylenediamine to develop multicolor nanomaterials with low toxicity, high stability, and high quantum yield. The distinctive electronic structures of CDs lead to the characteristic optical transitions, such as three colors of blue, green, and red, which are primarily attributed to the difference in configurations, despite the similar basic structures of conjugated systems. The excitation-independent emission and the single exponential decay of CDs indicate the single chromophore-like nature in each type of CD. In addition, the two-photon luminescence of CDs exhibits a comparable shape and time profile to the typical photoluminescence with high photostability. Although the surface-related defect states are observed by intragap excitation, the contribution of defect states is barely observed in the emission profile upon band gap excitation. Consequently, the controllability of optical transitions in CDs enhances the potential of tunable multicolor nanomaterials for various applications as alternatives to quantum dots containing toxic elements.

Branching ratio in photodissociation of 1-bromo-3-chlorobenzene cation.

A new and convenient calculation method based on Rice-Ramsperger-Kassel-Marcus (RRKM) theory assuming an extremely loose transition state (LTS) has been attempted to predict the branching ratio in photodissociation. This method enables estimation of the branching ratios without detailed structural information on the transition state which is indispensable in conventional RRKM calculations. To evaluate our simple method through comparison to the experimental results, photodissociation of 1-bromo-3-chlorobenzene cation (3BCB+) was chosen as a model unimolecular reaction system which has two distinct photodissociation channels in ultraviolet region: 3BCB+ → Br-dissociated daughter ion (ClBz+) + Br and 3BCB+ → Cl-dissociated daughter ion (BrBz+) + Cl. The branching ratio was monitored with decreasing the internal energy using a linear tandem time-of-flight mass spectrometer, which clearly showed decreased branching ratios of 3BCB+ → ClBz+ + Br over 3BCB+ → BrBz+ + Cl in reasonable agreement with the calculation results employing the new method. Although there was some discrepancy in internal energy between the experimental and calculation results, the new calculation method is worth to be extended to other diverse systems considering its intuitive and simple nature.

Dual wavelength lasing of InGaN/GaN axial-heterostructure nanorod lasers.

Optical confinement effects are investigated in InGaN/GaN axial-heterostructure nanolasers. Cylindrical nanorods with GaN/InGaN/GaN structures are prepared using combined processes of top-down and bottom-up approaches. The lasing of InGaN is observed at a low threshold (1 µJ cm-2), which is attributed to an efficient carrier transfer process from GaN to InGaN. The lasing of GaN is also found in the threshold range of 10-20 µJ cm-2 with a superlinear increase in emission intensity and high quality factors (Q = 1000), implying that dual wavelengths of lasing are tunable as a function of excitation intensity. The non-classical Fabry-Pérot modes suggest strong light-matter interactions in nanorods by optical confinement effects. The polarization of lasing indicates that the non-classical modes are in the identical transverse mode, which supports the formation of exciton-polaritons in nanorods. Polariton lasing in a single axial-heterostructure nanorod is observed for the first time, which proposes small-sized light sources with low threshold, polarized light, and tunable wavelengths in a single nanorod.

Structures and infrared photodissociation of [(aniline)-(methanol)-(water)2].

The structures of [(aniline)-(methanol)-(water)2]+ were investigated by infrared spectroscopy coupled with linear tandem mass spectrometry. We suggest the most stable structure of [(aniline)-(methanol)-(water)2]+ through infrared photodissociation spectra supported by the density functional theory calculations at the level of ωB97X-D/cc-pVQZ. Methanol and one water molecule formed hydrogen bonding with the amino group of aniline, while the other water formed hydrogen bonding with methanol. Upon infrared excitation of [(aniline)-(methanol)-(water)2]+, the water molecule connected to methanol turned out to be preferentially ejected, although the total internal energy in the cluster ion was large enough to dissociate other solvent molecules. This unique dissociation feature was attributed to the significant difference in the dissociation rates as obtained by the Rice-Ramsperger-Kassel-Marcus theory calculations as well as structural restriction.

Tuning Band Alignments and Charge-Transport Properties through MoSe2 Bridging between MoS2 and Cadmium Sulfide for Enhanced Hydrogen Production.

Transition-metal dichalcogenide materials play a major role in the state-of-the-art innovations for energy conversion because of potential applications resulting from their unique properties. These materials additionally show inordinate potential toward the progress of hygienic power sources to deal with increasing environmental disputes at the time of skyrocketing energy demands. Herein, we report earth-abundant, few-layered, MoSe2-bridged MoS2/cadmium sulfide (CdS) nanocomposites, which reduce photogenerated electron and hole recombination by effectively separating charge carriers to achieve a high photocatalytic efficiency. Accordingly, the MoSe2-bridged MoS2/CdS system produced effective hydrogen (193 µmol·h-1) as that of water using lactic acid as a hole scavenger with the irradiation of solar light. The presence of few-layered MoSe2 bridges in MoS2/CdS successfully separates photogenerated charge carriers, thereby enhancing the shuttling of electrons on the surface to active edge sites. To the best of our knowledge, this few-layered MoSe2-bridged MoS2/CdS system exhibits the most effective concert among altogether-reported MoS2-based CdS composites. Notably, these findings with ample prospective for the development of enormously real photocatalytic systems are due to their economically viable and extraordinary efficiency.

Structures of aniline(pyrrole)+, aniline(ethanol)+, and aniline-(benzene).

Molecular structures of aniline(pyrrole)+, aniline(ethanol)+, and aniline(benzene)+ produced via resonance two-photon ionization at 266 nm were analyzed by infrared predissociation spectroscopy coupled with tandem mass spectrometry. Structural optimization and frequency calculation using density functional theory were carried out to suggest the most probable isomers which are in good agreement with the observed infrared absorption spectra. Intermolecular bonds in the cluster ions were formed such that the electronegative oxygen atom of the solvent molecule or the pi electron of the aromatic ring forms a hydrogen bonding to NH of aniline.

Efficient and Stable CsPbBr3 Quantum-Dot Powders Passivated and Encapsulated with a Mixed Silicon Nitride and Silicon Oxide Inorganic Polymer Matrix.

Despite the excellent optical features of fully inorganic cesium lead halide (CsPbX3) perovskite quantum dots (PeQDs), their unstable nature has limited their use in various optoelectronic devices. To mitigate the instability issues of PeQDs, we demonstrate the roles of dual-silicon nitride and silicon oxide ligands of the polysilazane (PSZ) inorganic polymer to passivate the surface defects and form a barrier layer coated onto green CsPbBr3 QDs to maintain the high photoluminescence quantum yield (PLQY) and improve the environmental stability. The mixed SiN x/SiN xO y/SiO y passivated and encapsulated CsPbBr3/PSZ core/shell composite can be prepared by a simple hydrolysis reaction involving the addition of adding PSZ as a precursor and a slight amount of water into a colloidal CsPbBr3 QD solution. The degree of the moisture-induced hydrolysis reaction of PSZ can affect the compositional ratio of SiN x, SiN xO y, and SiO y liganded to the surfaces of the CsPbBr3 QDs to optimize the PLQY and the stability of CsPbBr3/PSZ core/shell composite, which shows a high PLQY (∼81.7%) with improved thermal, photo, air, and humidity stability as well under coarse conditions where the performance of CsPbBr3 QDs typically deteriorate. To evaluate the suitability of the application of the CsPbBr3/PSZ powder to down-converted white-light-emitting diodes (DC-WLEDs) as the backlight of a liquid crystal display (LCD), we fabricated an on-package type of tricolor-WLED by mixing the as-synthesized green CsPbBr3/PSZ composite powder with red K2SiF6:Mn4+ phosphor powder and a poly(methyl methacrylate)-encapsulating binder and coating this mixed paste onto a cup-type blue LED. The fabricated WLED show high luminous efficacy of 138.6 lm/W (EQE = 51.4%) and a wide color gamut of 128% and 111% without and with color filters, respectively, at a correlated color temperature of 6762 K.

Near-infrared electrochemiluminescence from orange fluorescent Au nanoclusters in water.

We report the unusual generation of near-infrared (near-IR) electrochemiluminescence (ECL) from water-soluble Au nanoclusters (NCs), of which the photoluminescence is primarily within the visible wavelength region. The near-IR ECL is ascribed to the Au(0)-glutathione motif in the Au NCs stabilized by glutathione in water.

Origin of highly efficient photoluminescence in AgIn5S8 nanoparticles.

The photoluminescence of AgIn5S8 nanoparticles was examined to clarify the emissive relaxation processes of defect states and to explain the highly efficient photoluminescence of defect states. The large Stokes shift of the defect emission was explained by strong electron-phonon coupling in the nanoparticles. Steady-state and time-resolved photoluminescence spectroscopy indicated two emissive defect states with characteristic emission energies and lifetimes. Change of the surface-to-volume ratio in the nanoparticles affected the relative contribution of the two states, implying that defect emission in higher energy was attributable to surface-related defects. The defect emission in lower energy was attributable to intrinsic defects, which were also present in bulk. The quantum yield of the surface defects was larger than that of the intrinsic defects, which accounted for the unusually high quantum yield of AgIn5S8 nanoparticles, although the origin of emission was the defect states, not the exciton recombination found in typical semiconductor nanoparticles.

Self-Assembled Tb3+ Complex Probe for Quantitative Analysis of ATP during Its Enzymatic Hydrolysis via Time-Resolved Luminescence in Vitro and in Vivo.

To more accurately assess the pathways of biological systems, a probe is needed that may respond selectively to adenosine triphosphate (ATP) for both in vitro and in vivo detection modes. We have developed a luminescence probe that can provide real-time information on the extent of ATP, ADP, and AMP by virtue of the luminescence and luminescence lifetime observed from a supramolecular polymer based on a C3 symmetrical terpyridine complex with Tb3+ (S1-Tb). The probe shows remarkable selective luminescence enhancement in the presence of ATP compared to other phosphate-displaying nucleotides including adenosine diphosphate (ADP), adenosine monophosphate (AMP), guanosine triphosphate (GTP), thymidine triphosphate (TTP), H2PO4- (Pi), and pyrophosphate (PPi). In addition, the time-resolved luminescence lifetime and luminescence spectrum of S1-Tb could facilitate the quantitative measurement of the exact amount of ATP and similarly ADP and AMP within living cells. The time-resolved luminescence lifetime of S1-Tb could also be used to quantitatively monitor the amount of ATP, ADP, and AMP in vitro following the enzymatic hydrolysis of ATP. The long luminescence lifetime, which was observed into the millisecond range, makes this S1-Tb-based probe particularly attractive for monitoring biological ATP levels in vivo, because any short lifetime background fluorescence arising from the complex molecular environment may be easily eliminated.

An oxygen-vacancy rich 3D novel hierarchical MoS2/BiOI/AgI ternary nanocomposite: enhanced photocatalytic activity through photogenerated electron shuttling in a Z-scheme manner.

An oxygen-vacancy rich, bismuth oxyiodide-based Z-scheme 3D hierarchical MoS2/BiOI/AgI ternary nanocomposite photocatalyst was fabricated using a simple precipitation process in ethylene glycol and water. The presence of oxygen-vacancies in BiOI and the two-dimensional nature of molybdenum disulfides in the composite prolongs the charge carrier lifetime through a Z-scheme system and enhances the performance of the photocatalyst for the degradation of rhodamine B. On the basis of efficient separation of photoexcited electron-hole pairs, a mechanism is proposed whereby MoS2 and oxygen vacancy states increase charge carrier lifetimes and improve the photocatalytic activity. The Z-scheme mechanism of the photocatalysis is consistent with the results of static and time-resolved photoluminescence, scavenging, and terephthalic acid photoluminescence experiments. Among the as-synthesized photocatalysts, the one containing 2 wt% of MoS2 in a composite of MoS2/BiOI/AgI exhibited the highest photocatalytic activity towards rhodamine B degradation, and its activity was 7 and 16 times higher than that of BiOI/AgI and BiOI, respectively. Degradation of phenol, the colorless model pollutant, was studied to confirm the visible-light photocatalytic performance of the MoS2/BiOI/AgI composite. This easily fabricated Z-scheme based MoS2/BiOI/AgI composite exhibits promising photocatalytic activity and will be useful for potential applications in energy and environmental areas.

Light-Matter Interactions in Cesium Lead Halide Perovskite Nanowire Lasers.

Light-matter interactions in inorganic perovskite nanolasers are investigated using single-crystalline cesium lead halide (CsPbX3, X = Cl, Br, and I) nanowires synthesized by the chemical vapor transport method. The perovskite nanowires exhibit a uniform growth direction, smooth surfaces, straight end facets, and homogeneous composition distributions. Lasing occurs in the perovskite nanowires at low thresholds (3 µJ/cm(2)) with high quality factors (Q = 1200-1400) under ambient atmospheric environments. The wavelengths of the nanowire lasers are tunable by controlling the stoichiometry of the halide, allowing the lasing of the inorganic perovskite nanowires from blue to red. The unusual spacing of the Fabry-Pérot modes suggests strong light-matter interactions in the reduced mode volume of the nanowires, while the polarization of the lasing indicates that the Fabry-Pérot modes belong to the same fundamental transverse mode. The dispersion curve of the exciton-polariton model suggests that the group refractive index of the polariton is significantly enhanced.

Unexpected Size Effect Observed in ZnO-Au Composite Photocatalysts.

Semiconductor-metal nanocomposites prepared with well-defined gold nanoclusters, such as Au25, Au144, and Au807, showed size-dependent photocatalytic activities for the reduction of nile blue and azobenzene. Whereas the photoreduction of nile blue was directly related with the charge separation and transfer rate from the photoexcited ZnO to gold nanoclusters, the photoreaction of azobenzene showed unexpected size effect with a clear threshold. Mechanistic investigations revealed that the photoreduction of azobenzene proceeded via a proton-coupled electron transfer process. The photocatalytic activity of the ZnO-Au nanocomposites was also dependent on the excitation intensity, demonstrating that the multielectron/multiproton process was controlled by the charge separation and transfer in the nanocomposites.

Chalcogenization-Derived Band Gap Grading in Solution-Processed CuIn(x)Ga(1-x)(Se,S)2 Thin-Film Solar Cells.

Significant enhancement of solution-processed CuIn(x)Ga(1-x)(Se,S)2 (CIGSSe) thin-film solar cell performance was achieved by inducing a band gap gradient in the film thickness, which was triggered by the chalcogenization process. Specifically, after the preparation of an amorphous mixed oxide film of Cu, In, and Ga by a simple paste coating method chalcogenization under Se vapor, along with the flow of dilute H2S gas, resulted in the formation of CIGSSe films with graded composition distribution: S-rich top, In- and Se-rich middle, and Ga- and S-rich bottom. This uneven compositional distribution was confirmed to lead to a band gap gradient in the film, which may also be responsible for enhancement in the open circuit voltage and reduction in photocurrent loss, thus increasing the overall efficiency. The highest power conversion efficiency of 11.7% was achieved with J(sc) of 28.3 mA/cm(2), V(oc) of 601 mV, and FF of 68.6%.

Reversible Halide Exchange Reaction of Organometal Trihalide Perovskite Colloidal Nanocrystals for Full-Range Band Gap Tuning.

In recent years, methylammonium lead halide (MAPbX3, where X = Cl, Br, and I) perovskites have attracted tremendous interest caused by their outstanding photovoltaic performance. Mixed halides have been frequently used as the active layer of solar cells, as a result of their superior physical properties as compared to those of traditionally used pure iodide. Herein, we report a remarkable finding of reversible halide-exchange reactions of MAPbX3, which facilitates the synthesis of a series of mixed halide perovskites. We synthesized MAPbBr3 plate-type nanocrystals (NCs) as a starting material by a novel solution reaction using octylamine as the capping ligand. The synthesis of MAPbBr(3-x)Clx and MAPbBr(3-x)Ix NCs was achieved by the halide exchange reaction of MAPbBr3 with MACl and MAI, respectively, in an isopropyl alcohol solution, demonstrating full-range band gap tuning over a wide range (1.6-3 eV). Moreover, photodetectors were fabricated using these composition-tuned NCs; a strong correlation was observed between the photocurrent and photoluminescence decay time. Among the two mixed halide perovskite series, those with I-rich composition (x = 2), where a sole tetragonal phase exists without the incorporation of a cubic phase, exhibited the highest photoconversion efficiency. To understand the composition-dependent photoconversion efficiency, first-principles density-functional theory calculations were carried out, which predicted many plausible configurations for cubic and tetragonal phase mixed halides.

Band gap grading and photovoltaic performance of solution-processed Cu(In,Ga)S2 thin-film solar cells.

The photophysical properties of CuInxGa1-xS2 (CIGS) thin films, prepared by solution-based coating methods, are investigated to understand the correlation between the optical properties of these films and the electrical characteristics of solar cells fabricated using these films. Photophysical properties, such as the depth-dependent band gap and carrier lifetime, turn out to be at play in determining the energy conversion efficiency of solar cells. A double grading of the band gap in CIGS films enhances solar cell efficiency, even when defect states disturb carrier collection by non-radiative decay. The combinational stacking of different density films leads to improved solar cell performance as well as efficient fabrication because a graded band gap and reduced shunt current increase carrier collection efficiency. The photodynamics of minority-carriers suggests that the suppression of defect states is a primary area of improvement in CIGS thin films prepared by solution-based methods.

Blue luminescence of dendrimer-encapsulated gold nanoclusters.

Direct evidence for the blue luminescence of gold nanoclusters encapsulated inside hydroxyl-terminated polyamidoamine (PAMAM) dendrimers was provided by spectroscopic studies as well as by theoretical calculations. Steady-state and time-resolved spectroscopic studies showed that the luminescence of the gold nanoclusters consisted largely of two electronic transitions. Theoretical calculations indicate that the two transitions are attributed to the different sizes of the gold nanoclusters (Au8 and Au13). The luminescence of the gold nanoclusters was clearly distinguished from that of the dendrimers.

MODE-specific deactivation of adenine at the singlet excited states.

The deactivation process of adenine excited near the band origin of the lowest ππ* state ((1)L(b)) is investigated using picosecond (ps) time-resolved photoionization spectroscopy. The transients obtained with a ps pump pulse at the sharp vibronic bands, 36,105 cm(-1) (D) and 36,248 cm(-1) (E), in the resonant two-photon ionization spectrum exhibit a bi-exponential decay with two distinct time constants of τ1 ~ 2 ps and τ2 > 100 ps, whereas the transients with the pump at other wavenumbers in this energy region show a single exponential decay with τ = 1-2 ps. We suggest that the τ1 represents the lifetimes of the (1)nπ∗ energy levels near the D and E peaks, which are excited together by the ps pump pulse having a broad spectral bandwidth, and the τ2 shows the lifetimes of D and E peaks. The long lifetime of D level is attributed to a small barrier for internal conversion from the minimum of the (1)L(b) state to the (1)nπ* state. On the other hand, the long lifetime of E level is ascribed to the nuclear configuration of adenine at this level, which is unfavorable to reach the seam of the conical intersection leading to nearly barrierless deactivation to the electronic ground state. This study shows that the ps time-resolved spectroscopy provides a powerful tool to study mode- and energy-specific deactivation processes occurring in a multi-dimensional potential energy surface.