Emission Spectra Research Articles

Circularly Polarized Luminescence from Pure and Eu-Doped Trigonal TbPO4·nH2O Nanocrystals.

In this contribution, we describe the preparation, by means of a precipitation reaction from aqueous solution at 40 °C, and the structural characterization of nanocrystalline powders of trigonal Tb1-xEuxPO4·nH2O (with x = 0, 0.005, 0.01, 0.05, and 0.1; n tentatively assigned as 0.67) which crystallize in the two possible P3121 or P3221 enantiomorphic space groups. While the volume of the crystal lattice is not significantly affected by the Tb3+/Eu3+ substitution, the average crystallite size seems to depend on the Eu3+ dopant concentration and ranges from 13 to 30 nm. The desired handedness of the crystals has been induced by using, during the synthesis, one of the two possible enantiomers of tartaric acid (l or d). The analysis of the luminescence excitation and emission spectra, together with the decay kinetics of the 5D4 Tb3+ excited state, suggests the presence of a very efficient Tb3+ → Eu3+ energy transfer process in the Eu3+-doped orthophosphates. Upon excitation of Tb3+ ions at 368 nm, the enantiomorphic powders grown with l- or d-tartaric acid (i.e., l-TbPO4·0.67H2O/d-TbPO4·0.67H2O, l-Tb0.995Eu0.005PO4·0.67H2O/d-Tb0.995Eu0.005PO4·0.67H2O, and l-Tb0.9Eu0.1PO4·0.67H2O/d-Tb0.9Eu0.1PO4·0.67H2O) exhibited mirror circularly polarized luminescence signals in the visible spectral region (in the green and/or in the red).

Optical Emission Spectra of Molecular Excitonic Polariton Computed at the First‐Principles Level QED‐TDDFT

In microcavity, strong coupling between light and molecules leads to the formation of hybrid excitations, i.e., the polaritons, or exciton‐polaritons. Such coupling may alter the energy landscape of the system and the optical properties of the material, making it an effective approach for controlling the light emission from molecular materials. However, due to the complexity of vibrational modes, spectroscopic calculations for organic exciton‐polaritons remain to be challenging. In this work, based on the linear‐response quantum‐electrodynamical time‐dependent density functional theory (QED‐TDDFT), we employ the thermal vibrational correlation function (TVCF) formalism to calculate the molecular optical spectrum of the lower polaritons (LP) at first‐principles level for three molecules, i.e., anthracene, distyrylbenzenes (DSB), and rubrene. The polaron decoupling effect is confirmed from our first‐principles computations. The theoretical emission spectra of LP provide fruitful insights for molecular and device design in microcavities that are otherwise hindered due to the lack of vibrational information.

Optical Emission Spectra of Molecular Excitonic Polariton Computed at the First‐Principles Level QED‐TDDFT

Optical Emission Spectra of Molecular Excitonic Polariton Computed at the First‐Principles Level QED‐TDDFT

Kinetic study of the reaction of thiophene-tocopherols with peroxyl radicals enlightenings the role of O˙⋯S noncovalent interactions in H-atom transfer.

Three new α-tocopherol thiophene derivatives were efficiently synthesized, characterized and used for the first time as chain-breaking antioxidants for the inhibition of the autoxidation of reference oxidizable substrates. The rate constant of the reaction with alkylperoxyl (ROO˙) radicals and the stoichiometry of radical trapping (n) for the thiophene-tocopherol compounds were determined by measuring the oxygen consumption during the autoxidation of styrene or isopropylbenzene, using a differential pressure transducer. The measurement of the reaction with ROO˙ radicals in an apolar solvent at 30 °C showed inhibition rate constants (kinh) in the order of 104 M-1 s-1. To rationalise the kinetic results, the effect of the thiophene ring on the H-atom donation by O-H groups of the functionalized tocopherols was investigated by theoretical calculations. The importance of noncovalent interactions (including an unusual O˙⋯S bond) for the stability of the conformers has been shown, and the O-H bond dissociation enthalpy (BDE(OH)) of these derivatives was determined. Finally, the photophysical properties of these new compounds were investigated to understand if the addition of thiophene groups changes the absorption or emission spectra of the tocopherol skeleton for their possible application as luminescent molecular probes.

Formation mechanism of bright and dark concentric-ring pattern in dielectric barrier discharge

In this work, a bright and dark concentric-ring pattern is reported in a dielectric barrier discharge for the first time. The spatiotemporal dynamics of the bright and dark concentric-ring pattern are investigated with an intensified charge-coupled device and photomultiplier tubes. The results indicate that the bright and dark concentric-ring pattern is composed of three concentric-ring sublattices. These are bright concentric-ring structures, dark concentric-ring structures and wider concentric-ring structures, respectively. The bright concentric-ring structures and dark concentric-ring structures are alternately distributed. The bright concentric-ring structures are located at the centre of the wider concentric-ring structures. The wider concentric-ring structures first form from the outer edge and gradually develop to the centre. The essence of all three concentric-ring structures is the individual discharge filaments. The optical emission spectra of different sublattices are acquired and analysed. It is found that the plasma parameters of the three concentric-ring sublattices are different. Finally, the formation mechanism of the bright and dark concentric-ring pattern is discussed.

Exploring the structural, optical and photoluminescence of novel terbium-doped barium borosilicate glasses for high-performance technologies

The production process involved the use of the melt-quenching approach to produce a series of barium borosilicate glasses with the specific chemical formula 55B2O3+(26-x)BaO+12SiO2+7Na2O + xTb4O7, where x = 0, 0.5, 1, 2, and 3 mol%. X-ray diffraction (XRD), Raman spectroscopy, optical absorption, and photoluminescence spectra measurement were used to examine the prepared samples. X-ray diffraction revealed the non-crystalline character of the assembled samples. The Raman spectroscopy revealed that the incorporation of Tb4O7 into borosilicate glasses induced alterations in their structure. As the doping of Tb3+ ions increases, the density and molar volume of the glasses under investigation increase. Furthermore, the ion concentration and field strength increase while the polaron radius and inter-ionic distance decrease. The glass optical absorption spectra showed five peaks in the wavelength range from 300 nm to 2000 nm: 5L10, 5D3, 5D4, 7F(0, 1, 2), and 7F3, attributed to Tb3+ ion electronic transitions. In addition, optical parameters like optical energy gap, Urbach energy, refractive index, molar refractive index, reflection loss, electronic polarizability, and optical transmission coefficient were computed. Terbium-doped borosilicate glasses had a decreased optical energy gap and an improved refractive index. Photoluminescence spectra were excited at 325 nm and showed five peaks in the range of 400–750 nm. Photoluminescence (PL) emission spectra exhibit distinct peaks in the visible range.

Effect of Al2O3/Ga2O3 ratio on the structure and luminescence properties of Sm3+ doped SrO-Nb2O5-Al2O3-Ga2O3-SiO2 glasses

The Sm3+ doped SrO-Nb2O5-Al2O3-Ga2O3-SiO2 glasses in this work were prepared using the conventional melt quenching method. The effects of Al2O3/Ga2O3 ratio on the structure and orange light emission properties were studied by XRD, Raman spectroscopy, spectrophotometer and J-O theory, respectively. With the increase of Al2O3 content, the absorption coefficient of the glass sample gradually increases, which might be attributed to an increase in non-bridged oxygen bonds caused by a change in the glass network structure. Under 403 nm excitation, the emission spectra show clear peaks at 602 nm and 649 nm, representing the 4G5/2 → 6H7/2, and 4G5/2 → 6H9/2 transitions, respectively. When the Al2O3/Ga2O3 ratio is 0.25, the sample luminescence intensity is the highest, and the emission cross section of A2 glass sample is 4.34 × 10−22 cm2. The CIE color coordinates, color purity, and color temperature values of all samples were determined, and they were all located in the orange-red light region. The experiments results reveal that the prepared silica-aluminum-gallium glasses has a potential application prospect in orange-red LEDs, solid state lasers and other fields.

Microscale Lateral Perovskite Light Emitting Diode Realized by Self-Doping Phenomenon.

High-definition near-eye display technology has extremely close sight distance, placing a higher demand on the size, performance, and array of light-emitting pixel devices. Based on the excellent photoelectric performance of metal halide perovskite materials, perovskite light-emitting diodes (PeLEDs) have high photoelectric conversion efficiency, adjustable emission spectra, and excellent charge transfer characteristics, demonstrating great prospects as next-generation light sources. Despite their potential, the solubility of perovskite in photoresist presents a hurdle for conventional micro/nano processing techniques, resulting in device sizes typically exceeding 50 μm. This limitation impedes the further downsizing of perovskite-based components. Herein, we propose a plane-structured PeLED device that can achieve microscale light-emitting diodes with a single pixel device size < 2 μm and a luminescence lifetime of approximately 3 s. This is accomplished by fabricating a patterned substrate and regulating ion distribution in the perovskite through self-doping effects to form a PN junction. This breakthrough overcomes the technical challenge of perovskite-photoresist incompatibility, which has hindered the development of perovskite materials in micro/nano optoelectronic devices. The strides made in this study open up promising avenues for the advancement of PeLEDs within the realm of micro/nano optoelectronic devices.

Collective photon emission in solid state environments: Concatenating non-Markovian and Markovian dynamics

Collective light emission and multiqubit dynamics of solid-state quantum emitters are affected both by their coupling to the light field and to lattice vibrations. The effect of phonons on quantum emitters is twofold: polaron formation is described by ultrafast non-Markovian dynamics, while slower dephasing is well described by exponential decay. Of the two temperature-dependent processes, the effect of the former on the collective emission and the entanglement decay of emitters is usually not modeled, and also the latter is sometimes neglected. Here we propose and compare two methods that are efficient also for several emitters: the first method concatenates the fast and slow phonon dynamics, and the second is the polaron method. For a single quantum emitter, we show that the dynamical equations are identical in both methods, while predictions for two or more emitters also agree very well. Both of our methods incorporate non-Markovian dynamics due to phonons demonstrating the temperature sensitivity of the collective photon emission. Utilizing a simplified Markovian model instead may not be accurate enough especially for quantum information applications: for example, we show how the Markovian model may considerably overestimate the two-emitter concurrence, except at very low temperatures. Our concatenation and polaron methods can be applied to an arbitrary number and type of quantum emitters, and beyond the bulk GaAs environment that we consider here. Especially the concatenation method can take phonon effects into account at the same computational cost as modeling the emitter-photon interaction alone. Finally, we present approximate analytical expressions for the collective emission spectrum for N emitters on a one-dimensional chain. Published by the American Physical Society 2024

Investigating crater formation in nanosecond laser ablation of aluminum foils

A nanosecond Nd:YAG laser was used to study the laser ablation of aluminum foil in the phase explosion regime at a laser intensity range of 0.63–3.61 ×1012W/cm2. Laser ablation and plasma characteristics were studied using microscopic ablation crater images, plasma emission spectra, and plasma plume images. Measured plasma density using a Stark width of Al I (396.2 nm) showed a strong linear correlation with crater size, with a Pearson correlation coefficient (r) of 0.97. To understand the origin of this linear correlation, plasma temperature was estimated using Bremsstrahlung emission from 512 to 700 nm. The estimated plasma temperature and aspect ratio of the plasma plume were negatively correlated, having r=−0.76. This negative correlation resulted from a laser-plasma interaction, which heated the plasma and increased its hydrodynamic length. The percentages of laser energy used for plasma heating (Ep/EL) and Al foil ablation (EAl/EL) were estimated from plasma temperature. Increased EAl/EL, such as crater size, with increasing laser intensity, confirms that greater mass ablation is the fundamental reason for the strong linear correlation between crater size and plasma density.

Investigating crater formation in nanosecond laser ablation of aluminum foils

A nanosecond Nd:YAG laser was used to study the laser ablation of aluminum foil in the phase explosion regime at a laser intensity range of 0.63–3.61 ×1012W/cm2. Laser ablation and plasma characteristics were studied using microscopic ablation crater images, plasma emission spectra, and plasma plume images. Measured plasma density using a Stark width of Al I (396.2 nm) showed a strong linear correlation with crater size, with a Pearson correlation coefficient (r) of 0.97. To understand the origin of this linear correlation, plasma temperature was estimated using Bremsstrahlung emission from 512 to 700 nm. The estimated plasma temperature and aspect ratio of the plasma plume were negatively correlated, having r=−0.76. This negative correlation resulted from a laser-plasma interaction, which heated the plasma and increased its hydrodynamic length. The percentages of laser energy used for plasma heating (Ep/EL) and Al foil ablation (EAl/EL) were estimated from plasma temperature. Increased EAl/EL, such as crater size, with increasing laser intensity, confirms that greater mass ablation is the fundamental reason for the strong linear correlation between crater size and plasma density.

Hot Carrier Temperature Dynamics in Semiconductor Nanostructures: Full Lineshape Modeling of Ultrafast Time-Resolved Emission Spectra

Hot Carrier Temperature Dynamics in Semiconductor Nanostructures: Full Lineshape Modeling of Ultrafast Time-Resolved Emission Spectra

Down-shifting in Ce3+- Tb3+ co-doped phosphate glasses for solar cells application

The Down-Shifting (DS) of UV photons into the visible range has been attracting much attention for lighting appliances and solar cells. This work reported the DS luminescence in Ce3+-Tb3+ co-doped phosphate glasses. Photoluminescence and decay curves were measured and analysed. According to the emission spectra, it was noticed a decrease in emission of the Ce3+ peak intensity and an increase of the Tb3+ visible emission intensity when the Tb3+ concentration is enlarged, indicating an energy transfer process from Ce3+ to Tb3+. Moreover, it was observed that the blue emission of Tb3+ decreases, while the green emission enhances by gradually increasing Tb3+ concentration. According to the decay curves of Tb3+, this result can be explained by cross-relaxation between Tb3+ ions. The experimental temporal evolution of the green emission of Tb3+ ions obtained under excitation of the Ce3+ ions at 280 nm is well simulated using a proposed model. In this way, the dynamics of the processes involved is perfectly understood and can be applied for solar cell applications. Therefore, the samples were placed over a solar cell and excited with UV excitation. In this excitation range, the silicon solar cell is not efficient, but the Ce3+ ions absorb this energy and transfer to the Tb3+ ions, which produce an intense visible emission. This emission is detected by the solar cell and produces photocurrent. In summary, the use of co-doped phosphate glass could enhance the current in a solar cell in the UV region.

Effects of specular reflectance in laser-induced breakdown of metals

We investigate the effects of specular reflection on the laser-induced breakdown (LIB) of copper, iron, and tungsten using fast photography and optical emission spectroscopy. The laser parameters include spot diameter ranging from 30.89 to 1589.33 μm, irradiance from 467.10 to 0.17 GW/cm2, with a single pulse of 6 ns duration and 21 mJ energy. As the laser spot defocuses, the plasma morphology changes from a single plasma near the target surface to a separated, independently evolving two-component plasma, and then to a single plasma suspended above. The defocusing distance for this transition is significantly influenced by specular reflectance. The separate plasma, comprising of a metallic component and an air component, occurs only under high specular reflectance conditions: ≥66.7% for copper, ≥51.4% for iron, and ≥44.9% for tungsten. The spectral emission of the metallic component initially increases and then decreases with reducing specular reflectance, due to a trade-off between enhanced surface absorption and reduced irradiance caused by surface roughening. LIB threshold irradiance increases with specular reflectance, rising from 0.31 to 1.22 GW/cm2 for copper, 0.24 to 0.70 GW/cm2 for iron, and 0.38 to 0.87 GW/cm2 for tungsten. These findings show the impact of sample pretreatment on LIB ignition and subsequent plasma evolution, offering insights into potential sources of inaccuracy in LIB applications.

Enhancing fractionation of terpenoids and terpenes in citrus essential oils by a biphasic extraction system

Efficient deterpenation of essential oils is crucial for obtaining high value-added products. In this work, a biphasic extraction system integrated with associative extraction was utilized to enhance fractionation of terpenoids and terpenes, where organic salt and organic solvent were employed as extractants in each phase. Ten different organic solvents were evaluated in terms of their phase behavior, extraction performance, and EHS-related properties. The positive or negative effect of organic solvents on biphasic extraction performance was elucidated through molecular dynamics simulations and FT-IR spectra analysis. The results indicate that an organic solvent lacking hydrogen bonding ability can reduce its interaction with organic salt or terpenoids, thereby exerting a positive contribution to biphasic extraction. For crude orange sweet essential oil, the biphasic system containing tetrabutylammonium chloride and n-hexane achieves a 6.2-fold concentration of terpenoids, demonstrating its effectiveness in enhancing extractive deterpenation of essential oil.

Optical emission characterization of an atmospheric pressure dielectric barrier discharge in nitrogen: Evolution of CN emissions during PTFE etching

AbstractThe present work investigates the etching of coated polytetrafluoroethylene (PTFE) films using an atmospheric pressure dielectric barrier discharge operating in nitrogen in a filamentary regime. For different treatment durations, the optical emission spectra were recorded over time. Most of the emissions are attributed to the N2 second positive system. The presence of CN is also observed, and its emissions rise with the exposure time of PTFE. This rise is attributed to the density of CN produced. The X‐ray photoelectron spectroscopy surface characterization suggests two etching regimes. This is linked with a change in slope in the intensity evolution of the optical emissions of the CN. At longer times, a fluorinated deposit on the electrode is observed, confirming a different nature of the etched material.

Optical emission characterization of an atmospheric pressure dielectric barrier discharge in nitrogen: Evolution of CN emissions during PTFE etching

AbstractThe present work investigates the etching of coated polytetrafluoroethylene (PTFE) films using an atmospheric pressure dielectric barrier discharge operating in nitrogen in a filamentary regime. For different treatment durations, the optical emission spectra were recorded over time. Most of the emissions are attributed to the N2 second positive system. The presence of CN is also observed, and its emissions rise with the exposure time of PTFE. This rise is attributed to the density of CN produced. The X‐ray photoelectron spectroscopy surface characterization suggests two etching regimes. This is linked with a change in slope in the intensity evolution of the optical emissions of the CN. At longer times, a fluorinated deposit on the electrode is observed, confirming a different nature of the etched material.

The wide spectral range characteristics and dynamic evolution of laser-produced tin plasmas

The energy levels and transitions of highly charged Sn ions are key data for analyzing emission spectra, radiative opacity, and conversion efficiency of laser-produced Sn plasmas. Temporally–resolved spectra in the 6–45-nm range were acquired via high-precision, spatio–temporally resolved techniques. In addition, the Cowan code, based on Hartree–Fock multi-configurational interactions, was used to perform structural calculations for Sn4+–Sn13+ ion spectra. Emission spectra in the 11–18-nm range were primarily attributed to Sn8+–Sn12+ ions, with transitions involving principal quantum numbers Δn=0 and Δn=1. Whereas, emission spectra in the 6–11-nm and 18–45-nm ranges were mainly attributed to Sn9+–Sn13+and Sn4+– Sn9+ions, with transitions involving principal quantum numbers Δn=1,2. Furthermore, Segmented simulations were conducted based on the assumptions of a normalized Boltzmann distribution among the excited states and a steady-state collisional-radiative model to explain the characteristics of the radiation spectra and variations in state parameters variations during laser-produced plasma expansion from the core to the outer periphery. A specific analysis was conducted on the temporal evolution of the electron temperature and density, while the charge state of the plasma was analyzed over the 6–18-nm range. Based on the spectral diagnostics, this work focused on the impact of non-uniformity in the expansion of the Sn plasma.

Harnessing liquid crystal attributes of near-unit photoluminescent benzothioxanthene photosensitizers: Photophysical profiling in solution, solid state, and polymer matrix embedding

Liquid crystals (LCs) have garnered significant attention for their unique optical and electrical properties, making them promising candidates in various technological applications such as smart displays, sensors, telecommunications, biomedicals or wearable electronics. In this study, we explore the potential of several highly emissive benzothioxanthene imide (BTI) derivatives as LC materials with a focus on their robustness and temperature-stable emission behavior. By tailoring the molecular structure of BTIs, we have accomplished exceptional emissive properties while maintaining the inherent advantages of LCs, such as their self-organizing ability and responsive nature. We describe the formation of enantiotropic liquid crystals whose mesomorphic properties dependent on the nature, length, and position of the side chain. Moreover, we have investigated the thermal stability of their emission spectra over a wide range of temperature, highlighting their potential use in demanding conditions where precise optical performances are critical. Our findings underscore the importance of molecular design in achieving highly emissive LC materials with enhanced robustness and temperature stability, opening new avenues for the use of BTI derivatives.

Improving the Two-Color Temperature Sensing Using Machine Learning Approach: GdVO4:Sm3+ Prepared by Solution Combustion Synthesis (SCS)

The gadolinium vanadate doped with samarium (GdVO4:Sm3+) nanopowder was prepared by the solution combustion synthesis (SCS) method. After synthesis, in order to achieve full crystallinity, the material was annealed in air atmosphere at 900 °C. Phase identification in the post-annealed powder samples was performed by X-ray diffraction, and morphology was investigated by high-resolution scanning electron microscope (SEM) and transmission electron microscope (TEM). Photoluminescence characterization of emission spectrum and time resolved analysis was performed using tunable laser optical parametric oscillator excitation and streak camera. In addition to samarium emission bands, a weak broad luminescence emission band of host VO43− was also observed by the detection system. In our earlier work, we analyzed the possibility of using the host luminescence for two-color temperature sensing, improving the method by introducing the temporal dependence in line intensity ratio measurements. Here, we showed that further improvements are possible by using the machine learning approach. To facilitate the initial data assessment, we incorporated Principal Component Analysis (PCA), t-Distributed Stochastic Neighbor Embedding (t-SNE) and Uniform Manifold Approximation and Projection (UMAP) clustering of GdVO4:Sm3+ spectra at various temperatures. Good predictions of temperature were obtained using deep neural networks. Performance of the deep learning network was enhanced by data augmentation technique.