Compounding Methylene Blue with Selenium-decorated Graphene Quantum Dots to Improve Singlet Oxygen Production for Photodynamic Therapy Application.

Graphene quantum dots (GQDs) are known as suitable material to be applied in different fields such as photodynamic therapy (PDT). Herein, GQDs were synthesized by the pyrolysis method and then decorated with selenium (Se). Afterward, they were combined with methylene blue (MB) to increase singlet oxygen generation as well as to apply them more effectively in the PDT method. Furthermore, GQDs were investigated by transmission electron microscope (TEM), photoluminescence spectrum (PL), Fourier-transform infrared spectroscopy (FTIR), field emission scanning electron microscope (FESEM), reactive oxygen species (ROS) measurement, and cytotoxicity measurement. GQDs showed no dependence on the excitation wavelength. The result of ROS measurement proves that the combination of GQD-Se and MB increases singlet oxygen production. Moreover, afterglow measurement approved the beneficial effect of GQD-Se on even deep and near skin tumor treatment. Cytotoxicity measurements under dark conditions, cell viability, and the side effects on human cells were determined by (3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide) (MTT) assay. Our findings show that under dark conditions, even high concentrations of nanoparticles have no significant effect on cell viability. These findings and the high biocompatibility of GQDs indicate the effective application of GQD-Se-MB in PDT.

Luminescence Dynamics of BaAl2O4:Eu2+ Phosphor.

We studied steady-state and time-resolved photoluminescence of Eu doped BaAl2O4 phosphor. The undoped BaAl2O4 sample shows a dominant blue emission band at ~ 428 nm and two secondary maxima at ~ 405 and 456 nm due to F-centre and aggregate defects such as F2 -centre. The samples after doping of Eu at 1-5% show additional emission bands at ~ 485 and 518 nm due to Eu2+ centre and a red emission band at ~ 657 nm is attributed to Eu3+ centre. The sample doped with 2% of Eu shows anomalous emission having the dominant peak at ~ 494 nm. The average luminescence lifetime of the emission band at ~ 428 nm in the undoped sample was estimated to be (3.29 ± 0.91) ns. The average luminescence lifetime of this emission band after doping of Eu was found to increase by 102 orders of magnitude. The intensity of the 428 nm blue emission band was found to quench after doping of Eu beyond 3%. The concentration quenching effect was attributed to dipole-quadrupole interaction. Further, a non-radiative fluorescence energy transfer mechanism from an extrinsic Eu2+ centre to an intrinsic F-centre is proposed to describe the luminescence dynamics of the samples.

Charge Transfer Modulation in Vanadium-Doped WS2 /Bi2 O2 Se Heterostructures.

The field of photovoltaics is revolutionized in recent years by the development of two-dimensional (2D) type-II heterostructures. These heterostructures are made up of two different materials with different electronic properties, which allows for the capture of a broader spectrum of solar energy than traditional photovoltaic devices. In this study, the potential of vanadium (V)-doped WS2 is investigated, hereafter labeled V-WS2 , in combination with air-stable Bi2 O2 Se for use in high-performance photovoltaic devices. Various techniques are used to confirm the charge transfer of these heterostructures, including photoluminescence (PL) and Raman spectroscopy, along with Kelvin probe force microscopy (KPFM). The results show that the PL is quenched by 40%, 95%, and 97% for WS2 /Bi2 O2 Se, 0.4 at.% V-WS2 /Bi2 O2 Se, and 2 at.% V-WS2 /Bi2 O2 Se, respectively, indicating a superior charge transfer in V-WS2 /Bi2 O2 Se compared to pristine WS2 /Bi2 O2 Se. The exciton binding energies for WS2 /Bi2 O2 Se, 0.4 at.% V-WS2 /Bi2 O2 Se and 2 at.% V-WS2 /Bi2 O2 Se heterostructures are estimated to be ≈130, 100, and 80 meV, respectively, which is much lower than that for monolayer WS2 . These findings confirm that by incorporating V-doped WS2 , charge transfer in WS2 /Bi2 O2 Se heterostructures can be tuned, providing a novel light-harvesting technique for the development of the next generation of photovoltaic devices based on V-doped transition metal dichalcogenides (TMDCs)/Bi2 O2 Se.

Processing and characterization of large area InP nanowire photovoltaic devices.

III-V nanowire (NW) photovoltaic devices promise high efficiencies at reduced materials usage. However, research has so far focused on small devices, mostly ≤1 mm2. In this study, the upscaling potential of axial junction InP NW photovoltaic devices is investigated. Device processing was carried out on a full 2″ wafer, with device sizes up to 1 cm2, which is a significant increase from the mm-scale III-V NW photovoltaic devices published previously. The short-circuit current density of the largest 1 cm2devices, in which 460 million NWs are contacted in parallel, is on par with smaller devices. This enables a record power generation of 6.0 mW under AM1.5 G illumination, more than one order of magnitude higher than previous III-V NW photovoltaic devices. On the other hand, the fill factor of the larger devices is lower in comparison with smaller devices, which affects the device efficiency. By use of electroluminescence mapping, resistive losses in the indium tin oxide (ITO) front contact are found to limit the fill factor of the large devices. We use combined light-beam induced current (LBIC) and photoluminescence (PL) mapping as a powerful characterization tool for NW photovoltaic devices. From the LBIC and PL maps, local defects can be identified on the fully processed devices.

Green synthesis-assisted copper nanoparticles using Aegle marmelos leaves extract: physical, optical, and antimicrobial properties.

In the present report, Aegle marmelos leaf powder was used to synthesize copper nanoparticles (CuNPs) using a simple and cost-effective method. A. marmelos leaves have various medicinal uses including for the treatment of diarrhoea, constipation, diabetes, cholera, skin diseases, earache, blood purification, heart problems, and so on. The plant biomolecules induce the reduction of Cu2+ ions to CuNPs and also act as a capping and stabilizing agent. The formation of CuNPs was confirmed using photoluminescence (PL) excitation and emission spectra on a Shimadzu RF-5301 PC spectrofluorophotometer and the absorbance spectra of a UV-visible spectrophotometer at different stages during the synthesis process. In addition, other properties of synthesized CuNPs were also investigated using X-ray diffraction, Fourier transform infrared spectroscopy, and transmission electron microscopy techniques. The average size of the synthesized CuNPs was in the range 20-40 nm. Furthermore, the synthesized NPs were also considered for an antimicrobial study against Gram-positive Staphylococcus aureus and Proteus, and Gram-negative Escherichia coli and Salmonella spp. using the agar well diffusion method. The zone of inhibition against the Gram-positive bacteria was greater than the zone of inhibition against the Gram-negative bacteria. These investigation results suggest that synthesized NPs are promising nanomaterials for use as antimicrobial agents.

Highly Bright Silica-Coated InP/ZnS Quantum Dot-Embedded Silica Nanoparticles as Biocompatible Nanoprobes.

Quantum dots (QDs) have outstanding optical properties such as strong fluorescence, excellent photostability, broad absorption spectra, and narrow emission bands, which make them useful for bioimaging. However, cadmium (Cd)-based QDs, which have been widely studied, have potential toxicity problems. Cd-free QDs have also been studied, but their weak photoluminescence (PL) intensity makes their practical use in bioimaging challenging. In this study, Cd-free QD nanoprobes for bioimaging were fabricated by densely embedding multiple indium phosphide/zinc sulfide (InP/ZnS) QDs onto silica templates and coating them with a silica shell. The fabricated silica-coated InP/ZnS QD-embedded silica nanoparticles (SiO2@InP QDs@SiO2 NPs) exhibited hydrophilic properties because of the surface silica shell. The quantum yield (QY), maximum emission peak wavelength, and full-width half-maximum (FWHM) of the final fabricated SiO2@InP QDs@SiO2 NPs were 6.61%, 527.01 nm, and 44.62 nm, respectively. Moreover, the brightness of the particles could be easily controlled by adjusting the amount of InP/ZnS QDs in the SiO2@InP QDs@SiO2 NPs. When SiO2@InP QDs@SiO2 NPs were administered to tumor syngeneic mice, the fluorescence signal was prominently detected in the tumor because of the preferential distribution of the SiO2@InP QDs@SiO2 NPs, demonstrating their applicability in bioimaging with NPs. Thus, SiO2@InP QDs@SiO2 NPs have the potential to successfully replace Cd-based QDs as highly bright and biocompatible fluorescent nanoprobes.

Spectroscopic analysis of Muga silk nanoparticles synthesized by microwave method.

Muga silk nanoparticles (MSNP) were synthesized using a microwave-assisted radiolysis method. The effect of microwave on the Muga protein secondary structures was analyzed. The evolution of the secondary structure from random coils to the ß-sheets was determined by using FTIR, circular dichroism and X-ray diffraction techniques. The results showed that Muga silk fibroin protein contained the primary structure in silk-I state. When the protein was irradiated with microwave, nanoparticle synthesis was possible having silk-II state imparting crystallinity. The silk nanoparticles were characterized by a particle size analyzer and found to be of ~240 nm in size. The optical properties of these nanoparticles were studied by UV-vis. spectroscopy and photoluminescence. For studying thermal properties, differential scanning calorimetry was performed that revealed early glass transition, which could be attributed to the presence of water and proteins. It also revealed that nanoparticles are thermally stable. Such studies are important for understanding more about the MSNP and would be beneficial for their further wide applications.

Large-Scale Plasmonic Hybrid Framework with Built-In Nanohole Array as Multifunctional Optical Sensing Platforms.

Light coupling with patterned subwavelength hole arrays induces enhanced transmission supported by the strong surface plasmon mode. In this work, a nanostructured plasmonic framework with vertically built-in nanohole arrays at deep-subwavelength scale (6 nm) is demonstrated using a two-step fabrication method. The nanohole arrays are formed first by the growth of a high-quality two-phase (i.e., Au-TiN) vertically aligned nanocomposite template, followed by selective wet-etching of the metal (Au). Such a plasmonic nanohole film owns high epitaxial quality with large surface coverage and the structure can be tailored as either fully etched or half-way etched nanoholes via careful control of the etching process. The chemically inert and plasmonic TiN plays a role in maintaining sharp hole boundary and preventing lattice distortion. Optical properties such as enhanced transmittance and anisotropic dielectric function in the visible regime are demonstrated. Numerical simulation suggests an extended surface plasmon mode and strong field enhancement at the hole edges. Two demonstrations, including the enhanced and modulated photoluminescence by surface coupling with 2D perovskite nanoplates and the refractive index sensing by infiltrating immersion liquids, suggest the great potential of such plasmonic nanohole array for reusable surface plasmon-enhanced sensing applications.

Enhanced Photoluminescence Properties of Low-Dimensional Eu3+-Activated Y4Al2O9 Phosphor Compared to Bulk for Solid-State Lighting Applications and Latent Fingerprint Detection-Based Forensic Applications.

In recent years, nanoscale phosphors have become vital in optoelectronic applications and to understand the improved performance of nanophosphors over bulk material, detailed investigation is essential. Herein, trivalent europium-activated Y4Al2O9 phosphors were developed by solid-state reaction and solvothermal reaction methods and their performance as a function of their dimension was studied for various applications. Under 394 nm optical excitation, the photoluminescence (PL) emission, excited state lifetime of the nanophosphor, exhibits greater performance than its bulk counterpart. The homogeneous spherical structure of the nanophosphors as compared with solid lumps of bulk phosphors is the basis for almost 40% of the enhancement in nanophosphors' intense red emission compared to the bulk. Moreover, the thermal stability of the nanophosphor is much better than the bulk phosphor, which clearly indicates a key advantage of nanophosphor. The superior performance of Eu3+-doped Y4Al2O9 nanophosphors over their bulk counterparts has been demonstrated for industrial phosphor-converted light-emitting diodes and visualization of latent fingerprint.

Effect of Distance on Photoluminescence Quenching and Proximity-Induced Spin-Orbit Coupling in Graphene/WSe2 Heterostructures.

Spin-orbit coupling (SOC) in graphene can be greatly enhanced by proximity coupling it to transition metal dichalcogenides (TMDs) such as WSe2. We find that the strength of the acquired SOC in graphene depends on the stacking order of the heterostructures when using hexagonal boron nitride ( h-BN) as the capping layer, i.e., SiO2/graphene/WSe2/ h-BN exhibiting stronger SOC than SiO2/WSe2/graphene/ h-BN. We utilize photoluminescence (PL) as an indicator to characterize the interaction between graphene and monolayer WSe2 grown by chemical vapor deposition. We observe much stronger PL quenching in the SiO2/graphene/WSe2/ h-BN stack than in the SiO2/WSe2/graphene/ h-BN stack and, correspondingly, a much larger weak antilocalization (WAL) effect or stronger induced SOC in the former than in the latter. We attribute these two effects to the interlayer distance between graphene and WSe2, which depends on whether graphene is in immediate contact with h-BN. Our observations and hypothesis are further supported by first-principles calculations, which reveal a clear difference in the interlayer distance between graphene and WSe2 in these two stacks.

Features of the Molecular Structure and Luminescence of Rare-Earth Metal Complexes with Perfluorinated (Benzothiazolyl)phenolate Ligands.

A set of Sc, Nd, Sm, Eu, Ho, Gd, Er, Yb complexes with perfluorinated 2-(benzothiazol-2-yl)phenolate ligands Ln(SONF)3(DME) were synthesized by the reactions of silylamides Ln[N(SiMe3)2]3 with phenol H(SONF). The structure of the initial phenol, Sc, and Er complexes was established using X-ray analysis, which revealed that the obtained compounds are mononuclear, in contrast to the binuclear non-fluorinated analogues [Ln(SON)3]2 synthesized earlier. All the obtained complexes, both in solid state and in tetrahydrofuran (THF) solutions, upon excitation by light with λex 395 or 405 nm show intense luminance of the ligands at 440-470 nm. The Eu complex also exhibits weak metal-centered emission in the visible region, while the derivatives of Sm luminesces both in the visible and in the infrared region, and Nd, Er, and Yb complexes emit in the near IR (NIR) region of high intensity. DFT (density functional theory) calculation revealed that energy of frontier orbitals of the fluorinated complexes is lower than that of the non-fluorinated counterparts. The level of highest occupied molecular orbital (HOMO) decreases to a greater extent than the lowest occupied molecular orbital (LUMO) level.

Effect of γ-irradiation on optical properties of Eu2 O3 -doped polystyrene polymer films.

In the present study, europium (III) oxide (Eu2 O3 )-doped polystyrene (PS) polymer films were synthesized using a solution-casting technique for different filler levels. These films were irradiated with 5, 25 and 50 kGy γ doses and characterized using various techniques, viz. X-ray diffraction (XRD), and UV-visible and photoluminescence (PL) spectroscopies as a function of composition level and radiation dose. The UV-visible spectra indicated a decrease in the optical direct band gap of composite films with increasing concentrations of dopant and radiation dose. The band gaps of composites obtained using Tauc's equation were found to be 4.38, 4.37, 4.36 and 4.34 eV for 0, 1, 3 and 5% Eu2 O3 -doped PS respectively, while the band gaps of 5% Eu2 O3 -doped PS polymer films irradiated with 5, 25 and 50 kGy were found to be 4.30, 4.26 and 4.21 eV, respectively. Photoluminescence (PL) emission spectra showed the characteristic peaks of Eu3+ at 595 nm, 612 nm and 617 nm with an excitation wavelength of 247 nm. The intensity of characteristic peaks of Eu3+ was observed to increase with increasing filler concentration, while it was found to decrease with increasing radiation dose. The polymer under study may be useful in accidental dosimetry. As photoluminescence studies are carried out after a gap of 200 h from irradiation and PL emission of γ-irradiated polymer yielded 10 times emission when compared with non-irradiated polymer.

Tuning Optical Signatures of Single- and Few-Layer MoS2 by Blown-Bubble Bulge Straining up to Fracture.

Emerging atomic layer semiconducting crystals such as molybdenum disulfide (MoS2) are promising candidates for flexible electronics and strain-tunable devices due to their ultrahigh strain limits (up to ∼20-30%) and strain-tunable bandgaps. However, high strain levels, controllable isotropic and anisotropic biaxial strains in single- and few-layer MoS2 on device-oriented flexible substrates permitting convenient and fast strain tuning, remain unexplored. Here, we demonstrate a "blown-bubble" bulge technique for efficiently applying large strains to atomic layer MoS2 devices on a flexible substrate. As the strain increases via bulging, we achieve continuous tuning of Raman and photoluminescence (PL) signatures in single- and few-layer MoS2, including splitting of Raman peaks. With proper clamping of the MoS2 crystals, we apply up to ∼9.4% strain in the flexible substrate, which causes a doubly clamped single-layer MoS2 to fracture at 2.2-2.6% strain measured by PL and 2.9-3.5% strain measured by Raman spectroscopy. This study opens new pathways for exploiting 2D semiconductors on stretchable substrates for flexible electronics, mechanical transducers, tunable optoelectronics, and biomedical transducers on curved and bulging surfaces.

Photoluminescence and thermoluminescence studies of CaAl2O4:Dy(3+) phosphor.

Calcium aluminate phosphors activated by Dy(3+) have been prepared by a combustion method at a temperature of 600°C. Photoluminescence (PL) and thermoluminescence (TL) properties of gamma-irradiated Dy-doped calcium aluminate were investigated. The PL spectrum shows a broad peak around 488 nm and 573 nm, under 347 nm excitation. Thermoluminescence studies were performed for different concentrations of Dy. Optimum intensity of photoluminescence was found for 0.02 mol% concentration of Dy. It was found that initially the peak TL intensity increases with increasing concentration of Dy in the CaAl2O4 host, attains a maximum value for 0.05 mol% concentration and decreases with further increase in the doping concentration due to concentration quenching.

Structural characterization of Er(3+),Yb(3+)-doped Gd2O3 phosphor, synthesized using the solid-state reaction method, and its luminescence behavior.

We report the synthesis and structural characterization of Er(3+),Yb(3+)-doped Gd2O3 phosphor. The sample was prepared using the conventional solid-state reaction method, which is the most suitable method for large-scale production. The prepared phosphor sample was characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), thermoluminescence (TL), photoluminescence (PL) and CIE techniques. For PL studies, the excitation and emission spectra of Gd2O3 phosphor doped with Er(3+) and Yb(3+) were recorded. The excitation spectrum was recorded at a wavelength of 551 nm and showed an intense peak at 276 nm. The emission spectrum was recorded at 276 nm excitation and showed peaks in all blue, green and red regions, which indicate that the prepared phosphor may act as a single host for white light-emitting diode (WLED) applications, as verified by International de I'Eclairage (CIE) techniques. From the XRD data, the calculated average crystallite size of Er(3+) and Yb(3+) -doped Gd2O3 phosphor is ~ 38 nm. A TL study was carried out for the phosphor using UV irradiation. The TL glow curve was recorded for UV, beta and gamma irradiations, and the kinetic parameters were also calculated. In addition, the trap parameters of the prepared phosphor were also studied using computerized glow curve deconvolution (CGCD).

Influence of thiol capping on the photoluminescence properties of L-cysteine-, mercaptoethanol- and mercaptopropionic acid-capped ZnS nanoparticles.

Mercaptoethanol (ME), mercaptopropionic acid (MPA) and L-cysteine (L-Cys) having -SH functional groups were used as surface passivating agents for the wet chemical synthesis of ZnS nanoparticles. The effect of the thiol group on the optical and photoluminescence (PL) properties of ZnS nanoparticles was studied. L-Cysteine-capped ZnS nanoparticles showed the highest PL intensity among the studied capping agents, with a PL emission peak at 455 nm. The PL intensity was found to be dependent on the concentration of Zn(2+) and S(2-) precursors. The effect of buffer on the PL intensity of L-Cys-capped ZnS nanoparticles was also studied. UV/Vis spectra showed blue shifting of the absorption edge.

Synthesis, characterization and optical studies of highly luminescent ZnS nanoparticles associated with hypromellose matrix as a green and novel stabilizer.

ZnS nanoparticles stabilized by a carbohydrate-based matrix, hypromellose (hydroxypropyl methylcellulose) were prepared via a wet chemical method. The nanocomposite was characterized by X-ray diffraction, transmission electon microscopy and Fourier transform infrared spectroscopy. X-Ray diffraction patterns revealed a zinc blende structure. Thermogravimetric analysis suggested that polymer attached to the surface decomposes at 700 °C. Absorption measurements were carried out and calculation of the diameter polydispersity index (DPI) suggests the formation of monodisperse nanoparticles. The optical properties of the as-prepared samples were studied by UV/vis spectroscopy and steady-state photoluminescence (PL) spectroscopy. The PL studies indicate the applicability of these nanoparticles as biocompatible sensors or luminescence markers in future.

Kinetically Controlled Self-Assembly of Ag Nanoclusters with Enhanced Luminescence.

Constructing self-assembly with definite assembly structure-property correlation is of great significance for expanding the property richness and functional diversity of metal nanoclusters (NCs). Herein, a well-designed liquid reaction strategy was developed through which a highly ordered nanofiber superstructure with enhanced green photoluminescence (PL) was obtained via self-assembly of the individual silver nanoclusters (Ag NCs). By visual monitoring of the kinetic reaction process using time-dependent and in situ spectroscopy measurements, the assembling structure growth and the structure-determined luminescence mechanisms were revealed. The as-prepared nanofibers featured a series of advantages involving a high emission efficiency, large Stokes shift, homogeneous chromophore, excellent photostability, high temperature, and pH sensibility. By virtue of these merits, they were successfully employed in various fields of luminescent inks, encryption and anticounterfeiting platforms, and optoelectronic light-emitting diode (LED) devices.

Narrow-Band Green-Emitting Hybrid Organic-Inorganic Eu (II)-Iodides for Next-Generation Micro-LED Displays.

Low-dimensional metal halide perovskites are an emerging class of light-emitting materials for LED-based displays; however, their B-site cations are confined to ns2, d5, and d10 metals. Here, the design of divalent rare earth ions at B-site is presented and a novel Eu(II)-based iodide hybrid is reported with efficient (PLQY ≈98%) narrow-band (FWHM ≈43 nm) green emission and high thermal stability (97%@150 °C). Owing to reduced lattice vibrations and shrunken average distance of Eu(II)-iodide bonds in the face-sharing 1D-structure, photoluminescence from Eu(II) 4f-5d transition appears along with elevated crystal-field splitting of 5d energy level. The Eu(II)-based iodide hybrid is further demonstrated for color-pure green phosphor-converted LEDs with a maximum brightness of ≈396 000 cd m-2 and photoelectric efficiency of 29.2%. High-resolution micrometer-scale light-emitting diode (micro-LED) displays (2540 PPI) via the solution-processed screen is also presented. This work thus showcases a compelling narrow-band green emitter for commercial micro-LED displays.

Optical, Structural, and Synchrotron X-ray Absorption Studies for GaN Thin Films Grown on Si by Molecular Beam Epitaxy.

GaN on Si plays an important role in the integration and promotion of GaN-based wide-gap materials with Si-based integrated circuits (IC) technology. A series of GaN film materials were grown on Si (111) substrate using a unique plasma assistant molecular beam epitaxy (PA-MBE) technology and investigated using multiple characterization techniques of Nomarski microscopy (NM), high-resolution X-ray diffraction (HR-XRD), variable angular spectroscopic ellipsometry (VASE), Raman scattering, photoluminescence (PL), and synchrotron radiation (SR) near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. NM confirmed crack-free wurtzite (w-) GaN thin films in a large range of 180-1500 nm. XRD identified the w- single crystalline structure for these GaN films with the orientation along the c-axis in the normal growth direction. An optimized 700 °C growth temperature, plus other corresponding parameters, was obtained for the PA-MBE growth of GaN on Si, exhibiting strong PL emission, narrow/strong Raman phonon modes, XRD w-GaN peaks, and high crystalline perfection. VASE studies identified this set of MBE-grown GaN/Si as having very low Urbach energy of about 18 meV. UV (325 nm)-excited Raman spectra of GaN/Si samples exhibited the GaN E2(low) and E2(high) phonon modes clearly without Raman features from the Si substrate, overcoming the difficulties from visible (532 nm) Raman measurements with strong Si Raman features overwhelming the GaN signals. The combined UV excitation Raman-PL spectra revealed multiple LO phonons spread over the GaN fundamental band edge emission PL band due to the outgoing resonance effect. Calculation of the UV Raman spectra determined the carrier concentrations with excellent values. Angular-dependent NEXAFS on Ga K-edge revealed the significant anisotropy of the conduction band of w-GaN and identified the NEXAFS resonances corresponding to different final states in the hexagonal GaN films on Si. Comparative GaN material properties are investigated in depth.