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In this study, the optical and structural properties of carbon dots (CDs) synthesized using a hydrothermal method were investigated. CDs were prepared from various precursors such as citric acid (CA), glucose, and birch bark soot. The SEM and AFM results show that the CDs are disc-shaped nanoparticles with dimensions of ~7 nm × 2 nm for CDs from CA, ~11 nm × 4 nm for CDs from glucose, and ~16 nm × 6 nm for CDs from soot. The TEM images of CDs from CA showed stripes with a distance of 0.34 nm between them. We assumed that the CDs synthesized from CA and glucose consisted of graphene nanoplates located perpendicular to the disc plane. The synthesized CDs contain oxygen (hydroxyl, carboxyl, carbonyl) and nitrogen (amino, nitro) functional groups. CDs have strong absorption in the ultraviolet region in the range of 200–300 nm. All CDs synthesized from different precursors displayed bright luminescence in the blue-green region of the spectrum (420–565 nm). We found that the luminescence of CDs depended on the synthesis time and type of precursors. The results show that the radiative transitions of electrons occur from two levels with energies ~3.0 eV and ~2.6 eV, which are due to the presence of functional groups. [ABSTRACT FROM AUTHOR]

The photoluminescence of Au(I) complexes is generally characterized by long radiative lifetimes owing to the large spin-orbital coupling constant of the Au(I) ion. Herein, we report three brightly emissive Au(I) coordination compounds, 1, 2a, and 2b, that reveal unexpectedly short emission lifetimes of 10–20 ns. Polymorphs 2a and 2b exclusively exhibit fluorescence, which is quite rare for Au(I) compounds, while compound 1 reveals fluorescence as the major radiative pathway, and a minor contribution of a microsecond-scale component. The fluorescent behaviour for 1–2 is rationalized by means of quantum chemical (TD)-DFT calculations, which reveal the following: (1) S0–S1 and S0–T1 transitions mainly exhibit an intraligand nature. (2) The calculated spin-orbital coupling (SOC) between the states is small, which is a consequence of overall small metal contribution to the frontier orbitals. (3) The T1 state features much lower energy than the S1 state (by ca. 7000 cm−1), which hinders the SOC between the states. Thus, the S1 state decays in the form of fluorescence, rather than couples with T1. In the specific case of complex 1, the potential energy surfaces for the S1 and T2 states intersect, while the vibrationally resolved S1–S0 and T2–S0 calculated radiative transitions show substantial overlap. Thus, the microsecond-scale component for complex 1 can stem from the coupling between the S1 and T2 states. [ABSTRACT FROM AUTHOR]

Novel ternary fluoro-germano-tellurite (GTS) glasses doped with Er3+ ions with 0.5 mol% and 1.0 mol% were fabricated by a conventional melt and quenching method and investigated using methods of optical spectroscopy. The room-temperature absorption spectrum was recorded and analyzed to determine radiative transition rates, radiative lifetimes, and branching ratios of Er3+ luminescence. Decay curves of Er3+ luminesccence were recorded and analyzed. Temperature dependences of emission spectra and absorption spectra in the region from RT (room-temperature) up to 675 K were studied in detail. The contribution of competing radiative and nonradiative processes to the relaxation of luminescent levels of Er3+ was assessed. Absolute and relative sensitivity were established utilizing the comprehensive model based on thermally coupled 2H11/2/4S3/2 excited states of erbium. The high quantum efficiency of the first erbium-excited state and value of gain coefficient indicate that GTS:Er glass system can be considered as conceivable NIR (near infrared) laser material as well. [ABSTRACT FROM AUTHOR]

In the optical energy gap, visible and near-IR emission of halide phosphate glasses with a composition of 40P2O5-30ZnO-20LiCl-10BaF2 in mol% doped with 3.5 × 104 ppm Pr2O3, referred to as PZLBPr, were synthesized. The UV-VIS-NIR and spectroscopic properties of these glasses were also predicted. The current glasses had broadband emission photoluminescence covering a wavelength range of 1250 to 1700 nm when excited at 455 nm. These bands for near-infrared emission luminescence relate to the transitions 1G4 → 3H5, 1D2 → 1G4, and 3H4 → 3F3, 3F4 in the optical telecommunication window. The significant PL emission wideband was caused by the radiative transition from Pr3+: 1D2 to 1G4. At 445 nm excitation, these glasses exhibited emission bands that corresponded to blue/reddish orange spectral ranges in visible ranges. The prepared glass has a high lasing quality factor (Ω4/Ω6 = 0.9), high optical energy (4.72 eV), and quantum efficiency = 87.3% with FWHM = 156 nm of transition emission from the 1D2 → 1G4 level. As a result, broadband near infrared optical amplifiers can be fabricated from the prepared glasses. [ABSTRACT FROM AUTHOR]

We report a comparative study of coordination behaviour of 2-(2-aminophenyl)benzothiazole (NH2-pbt) and its phosphorus-containing derivative, α-aminophosphine oxide (PCNH-pbt), towards zinc halides. The corresponding coordination compounds [Zn(L)2Hal2] (L = PCNH-pbt, Hal = Cl, 1 and Hal = Br, 2) and [Zn(L')Hal2] (L' = NH2-pbt, Hal = Cl, 3 and Hal = Br, 4) were obtained as single phases. As evidenced by single-crystal X-ray diffraction analysis, L' ligand coordinates to Zn in a chelate manner via two N atoms. Despite a similar coordination mode in complexes 3 and 4, the spatial geometry of the ligand differs notably, which implies a relatively high flexibility of NH2-pbt. The L ligand exhibits another coordination mode, binding with Zn only via the oxygen of the P=O group. The differences in the structures of NH2-pbt, 3 and 4, and their counterparts, PCNH-pbt, 1 and 2, induce differences in their solid-state photoluminescence properties. The former group of the compounds exhibits conventional single-band emission, while the latter group reveals two bands. The minor band at 450 nm is ascribed to a radiative transition for the regular amine species, while the major band at 520–550 nm can be associated either with the proton-transferred imine species (ESIPT mechanism) or with a charge transfer state (TICT) with a different geometry. [ABSTRACT FROM AUTHOR]

A high-luminescent, blue-light excitable europium(III) coordination complex, [Eu(µ2-OC2H5)(btfa)(NO3)(phen)]2phen (1) {btfa = benzoyl trifluoroacetone, phen = 1,10-phenantroline}, has been synthesized and investigated. The complex was characterized by infrared (IR) and photoluminescence (PL) spectroscopy. The PL emission spectra of powder samples registered in a range of 10.7–300 K exhibit characteristic metal-centered luminescence bands, assigned to internal radiative transitions of the Eu3+ ion, 5D1→7Fj and 5D0→7Fj (j = 0–4). The high-resolution spectrum of the transition 5D0→7F0 shows that it consists of two narrow components, separated by 0.96 meV, which indicates the presence in the matrix of two different sites of the Eu3+ ion. The splitting pattern of 5D0→7Fj (j = 0–4) transitions indicates that europium ions are located in a low-symmetry environment. The absolute quantum yield and the sensitization efficiency were determined to be 49.2% and 89.3%, respectively. The complex can be excited with low-cost lasers at around 405 nm and is attractive for potential applications in optoelectronics and biochemistry. [ABSTRACT FROM AUTHOR]

In this study, a series of well-crystallized Yb3+/Er3+/Tm3+-tridoped Y2O3-ZnO ceramic nano-phosphors were prepared using sol–gel synthesis, and the phosphor structures were studied using X-ray diffraction, scanning electron microscopy, and thermogravimetric analysis. The phosphors were well crystallized and exhibited a sharp-edged angular crystal structure and mesoporous structure consisting of 270 nm nano-particles. All phosphors generated blue, green, and red emission bands attributed to Tm: 1G4→3H6, Er: 2H11/2 (4S3/2)→4I15/2, and Er: 4F9/2→4I15/2 radiative transitions, respectively. Increasing in luminescent centers, weakening of lattice symmetry, and releasing of dormant rare earth ions can enhance all emissions. Er3+ can obtain energy from Tm3+ to enhance green and red emission. These colors can be tuned by optimizing the doping concentrations of the Er3+ ion. The color coordinates were adjusted by tuning both the Er3+ concentration and excitation laser pump power to shift the color coordinates and correlated color temperature. The findings of this study will broaden the potential practical applications of phosphors. [ABSTRACT FROM AUTHOR]

The design of the active region is one of the most crucial problems to address in light emitting devices (LEDs) based on III-nitride, due to the spatial separation of carriers by the built-in polarization. Here, we studied radiative transitions in InGaN-based LEDs with various quantum well (QW) thicknesses—2.6, 6.5, 7.8, 12, and 15 nm. In the case of the thinnest QW, we observed a typical effect of screening of the built-in field manifested with a blue shift of the electroluminescence spectrum at high current densities, whereas the LEDs with 6.5 and 7.8 nm QWs exhibited extremely high blue shift at low current densities accompanied by complex spectrum with multiple optical transitions. On the other hand, LEDs with the thickest QWs showed a stable, single-peak emission throughout the whole current density range. In order to obtain insight into the physical mechanisms behind this complex behavior, we performed self-consistent Schrodinger–Poisson simulations. We show that variation in the emission spectra between the samples is related to changes in the carrier density and differences in the magnitude of screening of the built-in field inside QWs. Moreover, we show that the excited states play a major role in carrier recombination for all QWs, apart from the thinnest one. [ABSTRACT FROM AUTHOR]

Abstract: The paper introduces general considerations on structural properties of aromatic, antiaromatic and non-aromatic conjugated systems in terms of potential energy along bond length alternation and distortion coordinates, taking as examples benzene, cyclobutadiene and cyclooctatetraene. Pentalene, formally derived from cyclooctatetraene by cross linking, is also considered as a typical antiaromatic system. The main interest is concerned with [n]annulenes and model [n]annulene molecular systems, n ranging from 10 to 18. The rich variety of conformational and configurational isomers and of dynamical processes among them is described. Specific attention is devoted to bridged [10]- and [14]annulenes in the ground and lowest excited states as well as to s-indacene and biphenylene. Experimental data obtained from vibrational and electronic spectroscopies are discussed and compared with ab initio calculation results. Finally, porphyrin, tetraoxaporphyrin dication and diprotonated porphyrin are presented as annulene structures adopting planar/non-planar geometries depending on the steric hindrance in the inner macrocycle ring. Radiative and non-radiative relaxation processes from excited state levels have been observed by means of time-resolved fluorescence and femtosecond transient absorption spectroscopy. A short account is also given of porphycene, the structural isomer of porphyrin, and of porphycene properties. [ABSTRACT FROM AUTHOR]

TiO2 nanoparticles doped with different amounts of Nd3+ (0.5, 1, and 3 wt.%) were synthetized by the sol–gel method, and evaluated as potential temperature nanoprobes using the fluorescence intensity ratio between thermal-sensitive radiative transitions of the Nd3+. XRD characterization identified the anatase phase in all the doped samples. The morphology of the nanoparticles was observed with SEM, TEM and HRTEM microscopies. The relative amount of Nd3+ in TiO2 was obtained by EDXS, and the oxidation state of titanium and neodymium was investigated via XPS and NEXAFS, respectively. Nd3+ was present in all the samples, unlike titanium, where besides Ti4+, a significantly amount of Ti3+ was observed; the relative concentration of Ti3+ increased as the amount of Nd3+ in the TiO2 nanoparticles increased. The photoluminescence of the synthetized nanoparticles was investigated, with excitation wavelengths of 350, 514 and 600 nm. The emission intensity of the broad band that was associated with the presence of defects in the TiO2, increased when the concentration of Nd3+ was increased. Using 600 nm for excitation, the 4F7/2→4I9/2, 4F5/2→4I9/2 and 4F3/2→4I9/2 transitions of Nd3+ ions, centered at 760 nm, 821 nm, and 880 nm, respectively, were observed. Finally, the effect of temperature in the photoluminescence intensity of the synthetized nanoparticles was investigated, with an excitation wavelength of 600 nm. The spectra were collected in the 288–348 K range. For increasing temperatures, the emission intensity of the 4F7/2→4I9/2 and 4F5/2→4I9/2 transitions increased significantly, in contrast to the 4F3/2→4I9/2 transition, in which the intensity emission decreased. The fluorescence intensity ratio between the transitions I 821 I 880 = F 5 / 2 4 I 4 9 / 2 F 4 3 / 2 I 4 9 / 2 and I 760 I 880 = F 4 7 / 2 I 4 9 / 2 F 4 3 / 2 I 4 9 / 2 were used to calculate the relative sensitivity of the sensors. The relative sensitivity was near 3% K−1 for I 760 I 880 and near 1% K−1 for I 821 I 880 . [ABSTRACT FROM AUTHOR]

The influence of erbium ion concentration on the optical properties of BaF2:ErF3 crystals was investigated. Four ErF3 concentration (0.05, 0.08, 0.15 and 0.5 mol% ErF3)-doped BaF2 crystals were obtained using the Bridgman technique. Room temperature optical absorption in the 250–850 nm spectral range was measured, and the photoluminescence (PL) and decay times were also investigated. The Judd–Ofelt (JO) approximation was used, taking into account four absorption peaks (at 377, 519, 653 and 802 nm). The JO intensity parameters, Ωt (t = 2, 4, 6), were calculated. The influence of the ErF3 concentration on the JO parameters, branching ratio, radiative transition probability and radiative lifetime were studied. The obtained results were compared with measured values and with those reported in the literature. Under excitation at 380 nm, the well-known green (539 nm) and red (668 nm) emissions were obtained. The calculated and experimental radiative lifetimes were in millisecond range for green and red emissions. The intensity of the PL spectra varied with the Er3+ ion concentration. The emission intensity increased linearly or exponentially, depending on the ErF3 concentration. Under excitation at 290 nm, separate to the green and red emissions, a new UV emission band (at 321 nm) was obtained. Other research has not reported the UV emission or the influence of ErF3 concentration on emission behavior. [ABSTRACT FROM AUTHOR]

Optical absorption spectra and luminescence spectra were recorded as a function of temperature between 295 K and 800 K for single crystal samples of Gd2SiO5:Dy3+, Lu2SiO5:Dy3+, LiNbO3:Dy3+, and Gd3Ga3Al2O12:Dy3+ fabricated by the Czochralski method and of YAl3(BO3)4:Dy3+ fabricated by the top-seeded high temperature solution method. A thermally induced change of fluorescence intensity ratio (FIR) between the 4I15/2→ 6H15/2 and 4F9/2 → 6H15/2 emission bands of Dy3+ was inferred from experimental data. It was found that relative thermal sensitivities SR at 350 K are higher for YAl3(BO3)4:Dy3+ and Lu2SiO5:Dy3+than those for the remaining systems studied. Based on detailed examination of the structural peculiarities of the crystals it was ascertained that the observed difference between thermosensitive features cannot be attributed directly to the dissimilarity of structural factors consisting of the geometry and symmetry of Dy3+ sites, the number of non-equivalent Dy3+ sites, and the host anisotropy. Instead, it was found that a meaningful correlation between relative thermal sensitivity SR and rates of radiative transitions of Dy3+ inferred from the Judd–Ofelt treatment exists. It was concluded that generalization based on the Judd–Ofelt parameters and luminescence branching ratio analysis may be useful during a preliminary assessment of thermosensitive properties of new phosphor materials. [ABSTRACT FROM AUTHOR]

Ternary quantum dots (QDs) are very promising nanomaterials with a range of potential applications in photovoltaics, light-emitting devices, and biomedicine. Despite quite intensive studies of ternary QDs over the last years, the specific relaxation channels involved in their emission mechanisms are still poorly understood, particularly in the corresponding core-shell nanostructures. In the present work, we have studied the recombination pathways of AgInS2 QDs stabilized with the ZnAgInS alloy layer and the ZnS shell (AIS/ZAIS/ZnS QDs) using time-resolved fluorescence spectroscopy. We have also investigated FRET in complexes of AIS/ZAIS/ZnS QDs and cyanine dyes with the absorption bands overlapping in the different regions of the QD emission spectrum, which allowed us to selectively quench the radiative transitions of the QDs. Our studies have demonstrated that FRET from QDs to dyes results in decreasing of all QD PL decay components with the shortest lifetime decreasing the most and the longest one decreasing the least. This research presents important approaches for the investigation of ternary QD luminescence mechanisms by the selective quenching of recombination pathways. These studies are also essential for potential applications of ternary QDs in photodynamic therapy, multiplex analysis, and time-resolved FRET sensing. [ABSTRACT FROM AUTHOR]

Ratiometric luminescence thermometry employing luminescence within the biological transparency windows provides high potential for biothermal imaging. Nd3+ is a promising candidate for that purpose due to its intense radiative transitions within biological windows (BWs) I and II and the simultaneous efficient excitability within BW I. This makes Nd3+ almost unique among all lanthanides. Typically, emission from the two 4F3/2 crystal field levels is used for thermometry but the small ~100 cm−1 energy separation limits the sensitivity. A higher sensitivity for physiological temperatures is possible using the luminescence intensity ratio (LIR) of the emissive transitions from the 4F5/2 and 4F3/2 excited spin-orbit levels. Herein, we demonstrate and discuss various pitfalls that can occur in Boltzmann thermometry if this particular LIR is used for physiological temperature sensing. Both microcrystalline, dilute (0.1%) Nd3+-doped LaPO4 and LaPO4: x% Nd3+ (x = 2, 5, 10, 25, 100) nanocrystals serve as an illustrative example. Besides structural and optical characterization of those luminescent thermometers, the impact and consequences of the Nd3+ concentration on their luminescence and performance as Boltzmann-based thermometers are analyzed. For low Nd3+ concentrations, Boltzmann equilibrium starts just around 300 K. At higher Nd3+ concentrations, cross-relaxation processes enhance the decay rates of the 4F3/2 and 4F5/2 levels making the decay faster than the equilibration rates between the levels. It is shown that the onset of the useful temperature sensing range shifts to higher temperatures, even above ~ 450 K for Nd concentrations over 5%. A microscopic explanation for pitfalls in Boltzmann thermometry with Nd3+ is finally given and guidelines for the usability of this lanthanide ion in the field of physiological temperature sensing are elaborated. Insight in competition between thermal coupling through non-radiative transitions and population decay through cross-relaxation of the 4F5/2 and 4F3/2 spin-orbit levels of Nd3+ makes it possible to tailor the thermometric performance of Nd3+ to enable physiological temperature sensing. [ABSTRACT FROM AUTHOR]