Optical Photoluminescence Research Articles

A study on the impact of [BO33−], [PO43−] and [SO42−] ions in normal cubic structures via structural and photoluminescence properties of Y2O3:Eu3+ phosphors

A series of Y2O3-AG: Eu3+ (where AG = Anionic Groups [PO43−, SO42− and BO33−]) nanophosphors were synthesized via a chemical combustion method and their structural and photoluminescence properties were investigated. The crystal structure and the surface morphology studies were analysed through the X-Ray powder diffraction (XRPD), Field-emission scanning electron microscopy (FE-SEM), Fourier-transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The XRD results showed that undoped Y2O3 phosphors crystalized in a cubic crystal structure, while the Y2O3-AG phosphors transformed from the pure Y2O3 cubic structures, except for SO42− based phosphor materials. The SEM micrographs showed that the particles were formed in the micrometer range with different sizes and shapes. The FTIR spectra revealed the presence of various structural groups in the Y2O3, Y2O3-AG: Eu3+ phosphors. Moreover, the optical diffuse reflectance spectroscopy (DRS) and photoluminescence (PL) properties were investigated. Using the DRS data, the optical band gap energy values were obtained from the Kubelka-Munk function theory. Upon 395 nm excitation, the Y2O3-AG: Eu3+ phosphors emitted red light at 615 nm wavelength. Among all the samples, the Y2O3-BO3: Eu3+ produced the highest intensity of red-light emission. The International Commission on Illumination color coordinates indicated that these phosphors are potential candidates for producing enhanced red color components in white light-emitting diode (W-LEDs) applications.

Optical monitoring of adsorption of chromium (VI) molecular anions, molecules and clusters on carbon nanomaterials

Search for efficient adsorbent materials for removal of hexavalent chromium compounds from environment is a topical technological problem. In this paper, the possibility of optical monitoring of the adsorption of chromium (VI) molecular compounds on the surface of carbon nanomaterials (CNM) is examined. Theoretical calculations of optical absorption spectra of CrO42- anions and molecular clusters of such anions with metals, n*K2CrO4 (n = 1, 2, 4) and MIICrO4 (MII = Zn, Cd, Pb) adsorbed on the surfaces of bare and doped carbon nanotubes and graphene are carried out by TD-DFT method. Results of calculations are compared with experimental data on optical transmission, diffuse reflection and photoluminescence of specially prepared samples containing chromate molecular compounds and particles adsorbed on CNM.It is shown that adsorption of CrO42- anions by CNM can be detected by the appearance of characteristic bands in diffuse reflectance spectra in 310–380 nm region. Nanoparticles of K2CrO4 crystal adsorbed on CNM reveal an additional luminescence band in 600–700 nm region, and it can be utilized in the monitoring of such adsorption. The effect of CNM surface on optical spectra of chromium (VI) molecular compounds is analyzed in terms of splitting of excited electronic states of quasi-tetrahedral CrO42- anions.

Luminescence features of Ho3+ , Er3+ and Tm3+ ions in red lead added non-conventional antimony oxide glass system.

In this study, a glass system based on heavy metal oxides, namely Pb3 O4 -Sb2 O3 -SiO2 , was prepared with Ho2 O3 , Er2 O3 , and Tm2 O3 as dopants. The prepared glass were characterized using X-ray diffraction (XRD) and infrared (IR) studies. The luminescence efficiencies of the three rare earth ions viz., Ho3+ , Er3+ , and Tm3+ in the glass system were investigated, specifically focusing on green (Ho3+ , Er3+ ), blue (Tm3+ ), and near-infrared (NIR) emissions. The optical absorption (OA) and photoluminescence (PL) spectra of RE mixed glass displayed strong bands in the visible and NIR regions, which were analyzed using the Judd-Ofelt (J-O) theory. The J-O coefficients (Ωλ ) were found to be in the order of Ω2 > Ω4 > Ω6 for all the three glass. Notably, the Tm3+ -doped glass exhibited the lowest Ω2 value, which was attributed to a larger degree of disorder in the glass network due to lower fractions of Sb5+ and Pb4+ ions that take part in the glass network forming. This conclusion was arrived based on the IR studies. Furthermore, the quantitative analysis of PL spectra and decay curves indicated that SbHo and SbEr glass were suitable for efficient green emission, while SbTm glass is a promising choice for blue laser emission.

A High-Nuclearity Copper Sulfide Nanocluster [S-Cu50] Featuring a Double-Shell Structure Configuration with Cu(II)/Cu(I) Valences.

This work represents an important step in the quest for creating atomically precise binary semiconductor nanoclusters (BS-NCs). Compared with coinage metal NCs, the preparation of BS-NCs requires strict control of the reaction kinetics to guarantee the formation of an atomically precise single phase under mild conditions, which otherwise could lead to the generation of multiple phases. Herein, we developed an acid-assisted thiolate dissociation approach that employs suitable acid to induce cleavage of the S-C bonds in the Cu-S-R (R = alkyl) precursor, spontaneously fostering the formation of the [Cu-S-Cu] skeleton upon the addition of extra Cu sources. Through this method, a high-nuclearity copper sulfide nanocluster, Cu50S12(SC(CH3)3)20(CF3COO)12 (abbreviated as [S-Cu50] hereafter), has been successfully prepared in high yield, and its atomic structure was accurately modeled through single-crystal X-ray diffraction. It was revealed that [S-Cu50] exhibits a unique double-shell structural configuration of [Cu14S12]@[Cu36S20], and the innermost [Cu14] moiety displays a rhombic dodecahedron geometry, which has never been observed in previously synthesized Cu metal, hydride, or chalcogenide NCs. Importantly, [S-Cu50] represents the first example incorporating mixed Cu(II)/Cu(I) valences in reported atomically precise copper sulfide NCs, which was unambiguously confirmed by XPS, EPR, and XANES. In addition, the electronic structure of [S-Cu50] was established by a variety of optical investigations, including absorption, photoluminescence, and ultrafast transient absorption spectroscopies, as well as theoretical calculations. Moreover, [S-Cu50] is air-stable and demonstrates electrocatalytic activity in ORR with a four-electron pathway.

Synthesis and optical properties of WS2 nanotubes with relatively small diameters

Tungsten disulfide (WS2) nanotubes exhibit various unique properties depending on their structures, such as their diameter and wall number. The development of techniques to prepare WS2 nanotubes with the desired structure is crucial for understanding their basic properties. Notably, the synthesis and characterization of multi-walled WS2 nanotubes with small diameters are challenging. This study reports the synthesis and characterization of small-diameter WS2 nanotubes with an average inner diameter of 6 nm. The optical absorption and photoluminescence (PL) spectra of the as-prepared nanotubes indicate that a decrease in the nanotube diameter induces a red-shift in the PL, suggesting that the band gap narrowed due to a curvature effect, as suggested by theoretical calculations.

Effect of Different Substitutions at the 1,7-Bay Positions of Perylenediimide Dyes on Their Optical and Laser Properties.

Perylenediimide (PDI) compounds are widely used as the active units of thin-film organic lasers. Lately, PDIs bearing two sterically hindering diphenylphenoxy groups at the 1,7-bay positions have received attention because they provide a way to red-shift the emission with respect to bay-unsubstituted PDIs, while maintaining a good amplified spontaneous emission (ASE) performance at high doping rates. Here, we report the synthesis of a series of six PDI derivatives with different aryloxy groups (PDI 6 to PDI 10) or ethoxy groups (PDI 11) at the 1,7 positions of the PDI core, together with a complete characterization of their optical properties, including absorption, photoluminescence, and ASE. We aim to stablish structure-property relationships that help designing compounds with optimized ASE performance. Film experiments were accomplished at low PDI concentrations in the film, to resemble the isolated molecule behaviour, and at a range of increasing doping rates, to investigate concentration quenching effects. Compounds PDI 10 and PDI 7, bearing substituents in the 2' positions of the benzene ring (the one contiguous to the linking oxygen atom) attached to the 1,7 positions of the PDI core, have shown a better threshold performance, which is attributed to conformational (steric) effects. Films containing PDI 11 show dual ASE.

Luminescence of Cr-doped β-Ga2O3 thin films

The results of investigation of optical excitation, photoluminescence (PL) and cathodoluminescence (CL) spectra in Cr-doped β-Ga2O3 thin films are presented. The broad bands due to the generation of electron-hole pairs and transitions from the 4А2 ground level to the 4Т1 and 4Т2 excited states in Cr3+ ions are observed in the photoexcitation spectra. The R-lines and phonon repetitions of R-lines are observed on the luminescence spectra against the background of a broad structureless band with a maximum around 700 nm, caused by the 4T2 – 4A2 transitions in Cr3+ ions. The crystal field force Dq was determined and the Stokes and anti-Stokes repetitions of R-lines were interpreted.

Influence of the Bismuth Content on the Optical Properties and Photoluminescence Decay Time in GaSbBi Films.

We report the optical properties of GaSbBi layers grown on GaSb (100) substrates with different bismuth contents of 5.8 and 8.0% Bi. Fourier-transform photoluminescence spectra were determined to identify the band gaps of the studied materials. Further temperature- and power-dependent photoluminescence measurements indicated the presence of localized states connected to bismuth clustering. Finally, time-resolved photoluminescence measurements based on single-photon counting allowed the determination of characteristic photoluminescence decay time constants. Because of the increasing bismuth content and clustering effects, an increase in the time constant was observed.

Size-Dependent Optical Properties of InP Colloidal Quantum Dots.

Indium phosphide colloidal quantum dots (CQDs) are the main alternative for toxic and restricted Cd based CQDs for lighting and display applications. Here we systematically report on the size-dependent optical absorption, ensemble, and single particle photoluminescence (PL) and biexciton lifetimes of core-only InP CQDs. This systematic study is enabled by improvements in the synthesis of InP CQDs to yield a broad size series of monodisperse core-only InP CQDs with narrow absorption and PL line width and significant PL quantum yield.

Synthesis and Study of Organic Nanostructures Fabricated by Inclusion of 2-Methylbenzimidazole Molecules in Nanotubes of Chrysotile Asbestos, Mesoporous Silica, and Nanopores of Borate Glasses.

New organic nanostructures were synthesized by introducing 2-methylbenzimidazole (MBI) molecules from a melt, gas phase, or alcoholic solution into nanosized voids of borate porous glasses (PG), nanotubes of chrysotile asbestos (ChA), and mesoporous silica (MS). The incorporation of MBI into borate glasses with different pore sizes is accompanied by the appearance of several phases formed by nanocrystallites which have a MBI crystal structure, but somewhat differ in lattice parameters. The size of some crystallites significantly exceeds the size of nanopores, which indicates the presence of long-scale correlations of the crystal structure. The size of MBI nanocrystallites in ChA was close to the diameter of nanotubes (D ~10 nm), which shows the absence of crystal structure correlations. The XRD pattern of mesoporous silica filled by MBI does not exhibit reflections caused by MBI and a presence of MBI was confirmed only by the analysis of correlation function. The incorporation of MBI molecules into matrices is observed through optical IR absorption spectroscopy (FTIR) and photoluminescence. Introducing MBI in ChA and MS is followed by the appearance of bright green photoluminescence, the spectral structure of which is analogous to MBI crystals but slightly shifted in the blue region, probably due to a quantum-size effect. The influence of MBI inclusion in PG and ChA on the permittivity, dielectric losses, conductivity, and parameters of their hopping conductivity is analyzed.

Optical absorption and luminescent behaviour of Ruddlesden-Popper type Sr2(Ce1-xFex)O4 (x = 0–1.0) oxides

An attempt has been made to synthesise iron-doped Sr2(Ce1-xFex)O4 (x = 0–1.0) oxides and characterized with regards to optical absorption and photoluminescence. It exhibits single (orthorhombic), dual (orthorhombic + tetragonal), and single (tetragonal) phase formation with x = 0–0.03, 0.05–0.80, and 0.90–1.0, respectively. The peaks observed at ∼2.71 and ∼2.44 eV (say; x = 0) in photoluminescent spectra are assigned to the charge transfer transition between Ce–O2 and Ce–O1, respectively. These states are arising due to the length difference between terminal and equatorial Ce–O bonds in the CeO6 octahedron. The composition Sr2FeO4 (x = 1.0) depicts peaks at 2.66 and 2.56 eV related to the charge transfer transition (CTT) between Fe–O of FeO6 octahedra. The excitation spectrum Sr2(Ce0.80Fe0.20)O4 exhibits two peaks around 5.84 and 4.90 eV related to the different Ce4+ - O2− distances in the lattice. Moreover, shifting of peaks refers to red shift in spectra and arises due to decrease in Ce–O bond length. The optical absorption peak at 261 nm (say; x = 0) is attributed to transitions from O(2p) to Ce(4f) in the O2− and Ce4+ states. The band gap decreases (3.73–3.59 eV) with iron, and supporting our photoluminescent spectra.

(Invited) Smart Molecular/2D Heterostructures

Graphene and other 2D materials are almost exclusively based on inorganic lattices. Except for the chemical functionalization of the surface of the 2D material, molecules have been scarcely considered in this area. Here I propose to create hybrid heterostructures by interfacing stimuli-responsive molecular systems with graphene and semiconducting transition metal dichalcogenides (MoS2 and WSe2). The aim is that of tuning the properties of the “all surface” 2D material via an active control of the hybrid interface. This concept will provide an entire new class of smart molecular/2D heterostructures, which may be at the origin of a novel generation of hybrid materials and devices of direct application in highly topical fields like electronics, spintronics and energy storage. As smart-molecular systems I will choose magnetic spin-crossover materials able to switch between two spin states upon the application of an external stimulus (temperature, light or pressure) [2]. This spin transition is always accompanied by a significant change of volume in the material (by ca. 10%), so it can generate strain in its surroundings. I will show that in these heterostructures the electronic properties of graphene and the optical photoluminescence of monolayers of semiconducting metal dichalcogenides can be switched by light or by varying the temperature due to the strain concomitant to the spin transition [3, 4].

Thermal conductivity of type-Ib HPHT synthetic diamond irradiated with electrons

The effect of irradiation with 3 MeV electrons and subsequent high-temperature annealing on the thermal conductivity κT of synthetic HPHT diamond containing impurity nitrogen at a concentration of about 100 ppm was studied at temperatures from 5 to 410 K. At each stage of the experiment, the optical absorption and photoluminescence spectra, magnetization and thermal conductivity were measured on two plates from the same diamond single crystal. Color centers and their concentration in different locations in the samples were determined from the optical spectra. The concentration of paramagnetic impurities in the samples was determined from the temperature and field dependencies of the paramagnetic magnetization. Thermal conductivity is suppressed by two orders of magnitude at temperatures from 35 to 50 K after irradiation to a fluence of 5×1018 cm−2. Annealing at a temperature of 1800° C restored the thermal conductivity of diamond at moderate and high temperatures, but not at temperatures below 120 K. The measured data on thermal conductivity were analyzed within the framework of the phenomenological Callaway model in order to understand the role of various phonon scattering processes and how it changes during irradiation and annealing.

Enhanced intensity of Raman signals from hexagonal boron nitride films

Optical spectroscopy is commonly used to study the properties of 2D materials. In order to obtain the best signal-to-noise ratio, it is important to optimize the incoupling of the excitation laser and, at the same time, reduce spurious light reflection. We performed Raman spectroscopy on exfoliated hexagonal boron nitride (hBN) flakes of different thicknesses, placed on a 300 nm SiO2 on Si substrate. By changing the hBN layer thickness, we found a specific thickness, where the Raman signals from the substrate and the hBN showed maximum intensity, whereas the backscattered laser light was suppressed. To explain the increased emission, we calculated the reflectivity and transmissivity of the full layer system (air, hBN, SiO2, and Si) as a function of hBN layer thicknesses for different excitation wavelengths (457, 532, and 633 nm), using the transfer-matrix algorithm. To compare theory with the experiment, we performed Raman measurements with these three different excitation wavelengths on different flakes and determined their thicknesses with AFM measurements. The experimental results are in good agreement with the calculations, which shows the importance of thin film interference to obtain optimum spectroscopic conditions. Since interference colors are easily visible in an optical microscope, this facilitates the choice of optimum flakes for a wide range of optical characterization techniques, including Raman, photoluminescence, and single defect spectroscopy.

Facile growth of perovskite nanoparticles confined on dimension-controlled Si nanorod arrays for various promising photophysical applications

In this study, a facile growth of hybrid perovskite nanoparticles (NPs) has been demonstrated on mesoporous, high-aspect ratio, morphology-controlled Si nanorod (NR) arrays. A generic method of directly confining perovskite nanocrystallites (average size <7 nm) on a mesoporous substrate without the use of colloidal stabilization was introduced. The perovskite NPs coated on dimension-and position-controlled Si NR arrays were systematically investigated by their various photophysical properties such as optical reflectance, cathodoluminescence (CL), and photoluminescence (PL) behaviors at both room temperature and low temperature. The dimension and position of the Si NR arrays were controlled by e-beam lithography followed by selective metal-assisted chemical etching (MACE). Organic-inorganic perovskite NPs were synthesized on the surface of Si NR array by spin coating of perovskite precursor solution and followed by annealing. The porous and rough sites on the surface of the NR arrays acted as nucleation centers for the formation of perovskite NPs. Due to the excitonic recombination of CH3NH3PbBr3, the NPs confined on the various NR templates exhibited strong PL emission in the 505–510 nm region. Furthermore, due to greater radiative recombination and lesser carrier trapping in the NPs, the PL and CL emission intensities of the perovskite NPs localized on the surface of the NR array were dramatically increased (PL enhancement factor ∼ 7.7, when NR aspect ratio ∼ 17.2) as compared to the bulk perovskite microcrystals. The low-temperature PL study revealed higher exciton binding energy of the NPs as compared to the bulk microcrystalline film. A systematic investigation revealed that the optical absorption, as well as the emission color of the perovskite NPs, can be tuned by the aspect ratio of the Si NR arrays. The results of our studies indicate the application of bandgap engineering of perovskite nanocrystals through confinement in a mesoporous, well-organized, regularly-ordered template as a powerful tool for tuning the emission wavelength in next-generation photonic sources. Furthermore, the important findings on the periodic array of photoactive nanoscale materials introduced in this manuscript may open up huge opportunities in numerous cutting-edge applications such as light emitting diode arrays, photodetector arrays, individually addressable devices, display devices with controlled pixel size and pixel density, etc.

Optical properties and tunable luminescence of Ce3+/Dy3+ doped lithium borate glasses for photonic applications

Optical absorption and photoluminescence properties of novel lithium borate glasses, (B2O3)-(MO)-(Li2O)–(Bi2O3) where M stands for Ca, Mg or Sr, doped with Dy and Ce ions have been investigated. The fundamental optical absorption edge of these materials is observed in the region of 315–390 nm, and depends on the nature of alkaline-earth metals used as network modifiers. The photoluminescence spectra of Dy-doped glasses reveal two intensive emission bands in the visible range, which correspond to 4F9/2→6H15/2 (486 nm) and 4F9/2→6H13/2 (580 nm) transitions of Dy3+ ions. Ce-doped glasses show one broad band in the visible range, which corresponds to the 2D →2F5/2 (340 nm) transition of Ce3+ ions. Three photoluminescence lines (980 nm, 1010 nm and 1150 nm) attributed to the Dy3+ ions electronic transitions are observed in the near-IR region of the spectrum for Dy-doped glasses, while only one at 1150 nm is observed for the Dy/Ce co-doped glasses. Peculiarities of excitation energy transfer between rare-earth activator ions are discussed. These glasses are shown to be a promising host matrix for rare-earth doping.

Enhanced charge generation and transfer properties on anatase nanodendrite array photo-electrodes for high-efficiency quantum dot sensitized solar cells

The loading amount of quantum dots and trap density are the significant issues for quantum dot sensitized solar cells. Anatase TiO2 nanodendrite array is employed as the photo-electrodes for the CuInS2 quantum dot sensitized solar cells instead of the traditional TiO2 nanowire array, which is prepared by two-step hydrothermal process. The excellent charge generation and charge separation properties have been exhibited by the CuInS2 quantum dots sensitized photo-electrodes based on the anatase TiO2 nanodendrite array, which are characterized by the optical absorption spectra and photoluminescence spectra. Meanwhile, the branches from anatase TiO2 nanodendrite array provide much more paths for charge transfer and reduce the charge recombination traps in photo-electrodes, which have provided excellent charge transfer property for the solar cells. As a result, higher current density can be obtained by anatase TiO2 nanodendrite array structure based CuInS2 quantum dot sensitized solar cells, which has exhibited the photovoltaic conversion efficiency enhancement from 4.7% to 5.48%.

High‐Performance Self‐Assembled ZnO Nanowrinkle Network Structured Photodetectors

Herein, the effect of prebake temperature on the surface structure of zinc oxide (ZnO) nanowrinkle structures formed in a sol–gel growth process for UV photodetection is demonstrated. The sol–gel solutions are spin‐coated on glass and c‐plane sapphire substrates, and the resulting ZnO films are subjected to prebake and crystallization processes at 800 °C for an hour. In the sol–gel process, the prebake process is crucial in forming the nanowrinkle structure on the surface of the ZnO film. The maximum nanowrinkle structure of ZnO film is achieved at the prebake temperature of 150 °C. In addition to the formation of the optimized nanowrinkle structure, the UV response of the photodetector is further enhanced through the prebake temperature control. The nanowrinkle network structure significantly improves the optical absorbance and photoluminescence characteristics of the ZnO film, leading to high photocurrent, photoresponsivity, and external quantum efficiency for UV light. The results demonstrate the potential of sol–gel‐derived ZnO photodetectors with nanowrinkle network structures for UV sensing applications.

Selective Thermal and Photocatalytic Decomposition of Aqueous Hydrazine to Produce H2 over Ag-Modified TiO2 Nanomaterial.

An Ag-modified TiO2 nanomaterial was prepared by a one-pot synthesis method using tetra butyl titanate, silver nitrate, and sodium hydroxide in water at 473 K for 3 h. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy were used to determine the structure and morphology of the synthesized Ag-modified TiO2 nanomaterial. The diffuse reflectance UV-visible and photoluminescence spectroscopy results revealed that metallic Ag nanoparticles decreased the optical band gap and photoluminescence intensity of the TiO2. In addition, the Raman peak intensity and absorbance were increased after Ag modification onto TiO2. The photocatalytic efficiency of the synthesized samples was tested for decomposition of aqueous hydrazine solution under visible light irradiation. The photocatalytic efficiency of Ag-modified TiO2 nanomaterials was higher than that of bare TiO2 and Ag metal NPs due to the synergistic effect between the Ag metal and TiO2 structures. In addition, the surface plasmon resonance (SPR) electron transfer from Ag metal particles to the conduction band of TiO2 is responsible for superior activity of TiO2-Ag catalyst. The Ag-modified TiO2 nanomaterials offered a 100% H2 selectivity within 30 min of reaction time and an apparent rate constant of 0.018 min-1 with an activation energy of 34.4 kJ/mol under visible light radiation.

Investigation on structural, thermal, electrical and optical properties of a new (OIH) material based Co(II)

At room temperature, a new compound with formula (C6H10(NH3)2)2[CoCl4]Cl2·H2O is successfully synthesized by slow evaporation technique. Then, it is characterized by X-ray diffraction to found that it crystallize in the monoclinic system, P21/c space group. The structure can be described by the alternation of organic and inorganic groups form a periodic 0-D network along the a axis. Hydrogen bonds have a crucial role in structure cohesion. In addition, this compound is characterized by infrared and Raman spectroscopy (FT-IR and FT-Raman), TG-DTG-DSC measurements in order to analyze the thermal behavior of the crystal and Hirshfeld surface (HS) analysis. The dielectric study was reported and reveals a good agreement with thermal measurements. Nyquist plots show a non-Debye type relaxation process and confirm that the complex impedance curves follow the Cole Cole law and the conductivity is assured by a hopping mechanism of H+ proton. The optical properties of the crystal were studied using optical absorption UV-visible and photoluminescence (PL) spectroscopy.