A comprehensive photoluminescence and mechanoluminescence analysis of ZnS:Mn2+ nano-phosphor with zinc blende structure is presented. The sample containing quantum dot-sized nanocrystallites were synthesized by the chemical precipitation method and shows excellent orange luminescence at ambient conditions related to the 4T1->6A1 transition. The sample shows stable and identical luminescence behavior under both UV and X-ray excitation at ambient conditions and also shows excellent self-powered mechanoluminescence properties. The pressure and temperature-induced luminescence mechanism of the phosphor is also established. The shift of the 4T1->6A1 luminescence band of Mn2+ with both pressure and temperature and the luminescence mechanism is explained via the d5 Tanabe Sugano diagram. The broad luminescence band of 4T1->6A1 transition shifts from visible to near-infrared range at a rate of -35.8 meV/GPa with the increase of pressure and it is subsequently quenched completely at a pressure of 16.41 GPa due to a reversible phase transition from zinc blende to rocksalt phase. The high-pressure and temperature-dependent decay kinetics measurements of the sample luminescence are al
The limited operational range of phase transition-based luminescence thermometers necessitates the exploration of new host materials exhibiting first-order structural phase transitions to broaden the applicability of this approach. Addressing this need, the present study investigates the spectroscopic properties of as a function of temperature. A thermally induced structural transition from the low-temperature orthorhombic phase to the high-temperature trigonal phase, occurring at approximately 430 K, significantly alters the spectroscopic properties of Eu3 ions. Specifically, a reduction in the number of Stark lines due to changes in the point symmetry of Eu3 ions enables the development of a ratiometric luminescence thermometer with sensitivity as high as K. Furthermore, it was demonstrated that increasing the concentration of Eu3 ions shifts the phase transition temperature, allowing for modulation of the thermometric performance of this luminescence thermometer. The findings presented here not only expand the repertoire of phase transition-based luminescence thermometers but also illustrate how the luminescence properties of Eu3 ions can be employed to accurately monitor struct
This work summarizes the main results of the operation of the International Program Luminescence of Cave Minerals of the commission on Physical Chemistry and Hydrogeology of Karst of UIS of UNESCO in the field of activators of speleothem luminescence. It discusses Activators of Luminescence in Speleothems as a source of major mistakes in the interpretation of luminescent paleoclimatic records. It demonstrates the existence of 6 types of luminescence of speleothems and cave minerals in dependence of the type of the luminescence center and its incorporation in the mineral. 24 different activators of photoluminescence of speleothem calcite and 11 of aragonite are studied. This paper demonstrates that it is impossible to produce reliable Paleotemperature or Past Precipitation records from luminescence of speleothems without establishing the organic origin of the entire luminescence of the particular sample.
One of the key parameters determining the performance of a luminescent thermometer is its relative sensitivity. In ratiometric luminescence thermometry, high relative sensitivity to temperature variations is typically achieved when the two monitored emission bands exhibit opposite thermal monotonicity. However, realizing a thermal enhancement in the luminescence intensity of one of the emission bands remains a significant challenge. In this study, we present a novel approach that leverages the synergistic effect of two phenomena: (1) the high thermal sensitivity of Mn4+ ion luminescence, and (2) a thermally induced structural phase transition in LaGaO3, which facilitates the enhancement of the luminescence signal from Tb3+ ions in the high-temperature phase of the host material. This dual effect not only led to an increased maximum relative sensitivity but also extended the temperature range over which the sensitivity exceeded 1% K-1. The highest recorded sensitivity was 4.5 K-1 at 400 K. Additionally, to the best of our knowledge, the luminescence of Mn4+ ions in the high-temperature phase of LaGaO3:Mn4+ was observed and reported here for the first time. The thermally induced modi
We analyse the morphological, structural and luminescence properties of self-assembled ZnO nanowires grown by chemical vapour transport on Si(001). The examination of nanowire ensembles by scanning electron microscopy reveals that a non-negligible fraction of nanowires merge together forming coalesced aggregates during growth. We show that the coalescence degree can be unambiguously quantified by a statistical analysis of the cross-sectional shape of the nanowires. The examination of the structural properties by X-ray diffraction evidences that the nanowires crystallize in the wurtzite phase, elongate along the c-axis, and are randomly oriented in plane. The luminescence of the ZnO nanowires, investigated by photoluminescence and cathodoluminescence spectroscopies, is characterized by two bands, the nearband-edge emission and the characteristic defect-related green luminescence of ZnO. The cross-correlation of scanning electron micrographs and monochromatic cathodoluminescence intensity maps reveals that: (i) coalescence joints act as a source of non-radiative recombination, and (ii) the luminescence of ZnO nanowires is inhomogeneously distributed at the single nanowire level. Spec
Photoluminescence and thermally stimulated luminescence of synthetic and natural (morion and smoky) $α$-quartz crystals doped with aluminum and alkali ions were studied. The photoluminescence spectrum is characterized with the main blue band around 400 nm (~ 3.1 eV). The corresponding luminescence center is based on a defect containing aluminum and alkali as compensators in natural and synthetic quartz crystals. Photoluminescence can be detected at high temperatures above 700 K. The thermal quenching activation energy is 0.15 eV and the frequency factor is 3 10$^7$ s$^{-1}$. In the samples with silver ions the main luminescence band is located at ~ 260 nm (~ 4.7 eV) with a time constant of ~ 37 $μ$s at 80 K, and in the samples with copper ions the PL band is at ~ 360 nm (~ 3.4 eV) with a time constant ~ 50 μs at 80 K. For luminescence associated with silver the energy of thermal quenching is 0.7 eV with a frequency coefficient of 1 10$^{14}$ s$^{-1}$, and for the luminescence related to copper, these parameters are 0.55 eV and 10$^{14}$ s$^{-1}$. The differences in intra-center luminescence properties of the same defect containing alkali ions or noble ions are based on differences
An effect of alloying of the monoclinic beta- Ga2O3 with Al2O3 and In2O3 on the photoluminescent, thermoluminescent and persistent luminescent properties of Cr3+ ions has been comprehensively investigated. For this purpose, various series of Cr3+ and Ca2+ co-doped microcrystalline phosphors were synthesized by the solution combustion method, including pseudobinary compounds like (Ga-Al)2O3 with up to 20% Al and (Ga-In)2O3 with up to 50% In as well as pseudoternary compounds (Ga Al In)2O3 with balanced proportion of Al, Ga and In. The phase composition and crystal structure of the obtained materials were examined by X-ray powder diffraction technique. Detailed luminescence studies were conducted for the (Ga-Al)2O3 and (Ga-In)2O3 compounds which exhibited a single-phase monoclinic structure. Low-temperature and time-resolved photoluminescence investigations of the Cr-doped pseudobinary compounds unveiled several types of Cr3+ centres, attributed to the Al-, Ga- and In-centred octahedra in the studied alloys. The obtained results underscore the benefit of bandgap engineering through alteration in the host lattice chemical composition for efficient tuning of the thermoluminescent and p
Results of spectroscopic studies at ambient and high pressures of a LuAlO3:Ce3+ (LuAP:Ce) single crystalline film (SCF) as well as LuAP:Ce and YAlO3:Ce (YAP:Ce) single crystals are reported. Room temperature absorption measurements of the single crystals in the vacuum UV region allowed establishing the bandgap energies of 7.63 eV for YAP and 7.86 eV for LuAP, with an assumption of the direct band-gaps. Luminescence of Ce3+ in LuAP and YAP bulk crystals was measured as a function of temperature from 6 K up to 873 K. Temperature quenching of the Ce3+ luminescence in YAP:Ce was observed above 650 K, which is related to the location of the lowest Ce3+ 5d level at 1.27 eV below the conduction band minimum. No temperature quenching occurred in LuAP:Ce up to 873 K, mostly due to the lower energy of the 4f levels with respect to the valence band maximum. The barycenter energies and splittings of Ce3+ 5d states in YAP and LuAP at room temperature were precisely established. Theoretical calculations of the Ce3+ 5d states energy structure under pressure revealed a discrepancy between the obtained experimental results and the prediction of Dorenbos' theoretical model. The discrepancy can be re
The luminescence and Raman spectra of the Cs2ZrCl6 crystal in a wide range of pressures were studied in this work for the first time. Luminescence measurements were performed up to 10 GPa, while the Raman spectra were measured up to 20 GPa. The luminescence data revealed a linear blue shift of the emission maximum from about 2.5 eV at ambient pressure to 3.1 eV at 5 GPa and a strong intensity quenching. The indirect-to-direct bandgap transition at about 5 GPa, a phenomenon previously predicted only theoretically, was used to explain the strong quenching of the luminescence. This model was confirmed by fitting luminescence intensity data and analysis of the luminescence decay kinetics, which exhibited a shortening of the pulse decay time with the pressure increase. Raman spectra confirmed the stability of Cs2ZrCl6 up to 20 GPa and showed no evidence of the pressure-induced structural phase transitions. An energetic scheme of excitonic levels, which takes into account the indirect-to-direct band gasp transition, was proposed to explain the rapid luminescence quenching with increasing pressure.
Recent results on the study of spontaneous and stimulated luminescence of solid nitrogen in the near-infrared NIR range are presented. Irradiation was performed with an electron beam of subthreshold energy in the dc mode. Three series of experiments were performed: (i) measurement of cathodoluminescence CL at different electron energies on samples of different thicknesses, (ii) measurements of thermally stimulated luminescence TSL in combination with thermally stimulated exoelectron emission TSEE from pre-irradiated samples and (iii) recording of non-stationary luminescence curves NsL at selected wavelengths during gradual heating of samples under an electron beam. Three emission bands were recorded in the NIR TSL spectra of solid N$_2$: 794, 802, and 810 nm which form the $γ$-group. The band at 810 nm in stimulated luminescence was detected for the first time. The positions of all three spectral features coincide in the spectra of spontaneous and stimulated luminescence, as evidenced by a comparison of the CL spectrum recorded at 5 K with the TSL spectrum recorded at the TSL maximum at 16 K. The glow curves measured for these 3 bands were found to correlate with each other and wit
To develop a more universal luminescent thermometer that provides both high relative sensitivity and the ability to measure temperature across different spectral ranges and excitation wavelengths, the K3Yb(PO4)2:Eu3+ system was proposed in this work. It was demonstrated that this material undergoes a structural phase transition from the monoclinic to the hexagonal phase above 450 K. This transition enabled the construction of a ratiometric, phase-transition-based thermometer utilizing the luminescence intensity ratio of Stark lines of Eu3+ and Yb3+ ions, which exhibit SRmax values of 4.2% K^-1 and 1.15% K^-1, respectively. Moreover, increasing the Eu3+ ion concentration was shown to raise the phase transition temperature, thereby shifting the thermal operating range of both luminescent thermometers. Under 980 nm excitation, K3Yb(PO4)2:Eu3+ exhibits both cooperative luminescence from Yb3+ pairs and up-conversion emission from Eu3+ ions. Increasing the Eu3+ concentration enhances the Eu3+ luminescence intensity relative to the cooperative luminescence of Yb3+ pairs, resulting in a change in the emitted light color. The difference in the thermal quenching behavior of these two signals
The luminescence properties of the $\mathrm{[UO_2Cl_4]^{2-}}$ complex in an organic phase, especially the influence of large organic counter cations, have been studied by time-resolved laser-induced fluorescence spectroscopy (TRLFS) and ab initio modeling. The experimental spectrum was assigned by vibronic Franck-Condon calculations on quantum chemical models based on relativistic density functional approaches. The shape of the luminescence spectrum of the uranyl tetrachloride complex is determined by symmetrical vibrations and geometrical change upon emission. The possible change of the luminescence properties depending on the first and second uranyl coordination sphere was predicted theoretically for $\mathrm{[UO_2Br_4]^{2-}}$ and $\mathrm{[R_4N]_2[UO_2Cl_4]}$ ($\mathrm{R_4N}$ = $\mathrm{[Bu_4N]}$, $\mathrm{[{A336}]}$) systems. The computations reveal that for U(VI), the second coordination sphere has little influence on the spectrum shape, making speciation of uranyl complexes with identical first coordination-sphere ligands tedious to discriminate. The computed structural changes agreed well with experimental trends; theoretical spectra and peaks attribution are in a good accor
We generalize and systematize basic experimental data on optical and luminescence properties of ZnO single crystals, thin films, powders, ceramics, and nanocrystals. We consider and study mechanisms by which two main emission bands occur, a short-wavelength band near the fundamental absorption edge and a broad long-wavelength band, the maximum of which usually lies in the green spectral range. We determine a relationship between the two luminescence bands and study in detail the possibility of controlling the characteristics of ZnO by varying the maximum position of the short-wavelength band. We show that the optical and luminescence characteristics of ZnO largely depend on the choice of the corresponding impurity and the parameters of the synthesis and subsequent treatment of the sample. Prospects for using zinc oxide as a scintillator material are discussed. Additionally, we consider experimental results that are of principal interest for practice.
Cosmic ray detectors use air as a radiator for luminescence. In water and ice, Cherenkov light is the dominant light producing mechanism when the particle's velocity exceeds the Cherenkov threshold, approximately three quarters of the speed of light in vacuum. Luminescence is produced by highly ionizing particles passing through matter due to the electronic excitation of the surrounding molecules. The observables of luminescence, such as the wavelength spectrum and decay times, are highly dependent on the properties of the medium, in particular, temperature and purity. The results for the light yield of luminescence of previous measurements vary by two orders of magnitude. It will be shown that even for the lowest measured light yield, luminescence is an important signature of highly ionizing particles below the Cherenkov threshold. These could be magnetic monopoles or other massive and highly ionizing exotic particles. With the highest observed efficiencies, luminescence may even contribute significantly to the light output of standard model particles such as the PeV IceCube neutrinos. We present analysis techniques to use luminescence in neutrino telescopes and discuss experiment
Among the host materials luminescence the luminescence of the self-trapped exciton (STE) is reviewed. This luminescence, which band is situated at 2.6 to 2.7 eV, could be observed mainly under ionising radiation with energetic yield about 0.2. The STE does not participate in pure recombination processes. Host material defect luminescence at 5 eV appears in alpha-quartz after heavy irradiation. It is constituted of permanent defect after neutron irradiation and transient defect after dens electron beam irradiation. This luminescence could be observed well at temperatures below 60 K. All another luminescence are of impurity nature. The Ge impurity luminescence in alpha-quartz explained as STE near Ge. The aluminium and alkali complexes. One of them is with UV band at 6 eV, appears at low temperatures and could be excited only in tunnelling recombination process between pairs (AlO4 Me), where Me is an alkali ion captured an electron and a hole remains on aluminium tetrahedron. Another luminescence with band at 3.4 eV is also luminescence of complexes (AlO4 Me), which behaviour is similar to the luminescence of alkali alumosilicate glass. The third luminescence with band at 3 eV could
We have developed a non-Markovian theory of the polariton luminescence taking the molecular vibrations into account. The calculations were made in the polariton basis. We have shown that the frequency shift and the polariton spectral lines broadening strongly depend on the frequency-dependent exciton contribution to the polariton. In the single-mode microcavity our non-Markovian theory predicts the Fano resonances in the polariton luminescence, and also narrowing of the spectral lines with the increase of the total number of molecules in the case of the intramolecular nature of the low frequency vibrations. The theory enables us to consider a non-equilibrium (hot) exciton-polariton luminescence similar to the hot luminescence of molecules and crystals. This opens a way for its observation in organic-based nanodevices.
A spontaneous luminescence is reported when epoxy resin samples are heated in air. This phenomenon is very sensitive to the nature of the atmosphere. The same treatment in nitrogen leads to an extinction of the luminescence. The emission process is restored when samples are kept for a sufficient time in air. In order to better understand this phenomenon, we have investigated the luminescence of the elementary constituents of the epoxy (resin and hardener) when heated in air and nitrogen, as well as during resin curing in the same atmospheres. It appears that the emission process is linked with the presence of oxygen. Although the kinetics of the luminescence can differ depending on the nature of the sample (cured resin, resin during curing, liquid components), the emission spectra are the same during resin curing and upon heating of the cured resin and hardener. The emission spectrum of the base resin is different. It is concluded that the light results from a chemiluminescence process during oxidation.
This study investigates the effect of hydrostatic pressure on the luminescence properties of CsPbBr3 single crystals at 12 K. The luminescence at the edge of the band gap reveals a structure attributed to free excitons, phonon replica of the free excitons, and Rashba excitons. Changes in the relative intensity of the free and Rashba excitons were observed with increasing pressure, caused by changes in the probability of nonradiative deexcitation. At pressures around 3 GPa, luminescence completely fades away. The red shift of the energy position of the maximum luminescence of free and Rashba excitons in pressure ranges of 0-1.3 GPa is attributed to the length reduction of Pb-Br bonds in [PbBr6]4- octahedra, while the high-energy shift of the Rashba excitons at pressures above 1.3 GPa is due to [PbBr6]4- octahedra rotation and changes in the Pb-Br_Pb angle.
Chemical defects in polyethylene (PE) can deleteriously downgrade its electrical properties and performance. Although these defects usually leave spectroscopic signatures in terms of characteristic luminescence peaks, it is nontrivial to make unambiguous assignments of the peaks to specific defect types. In this work, we go beyond traditional density functional theory calculations to determine defect-derived emission and absorption energies in PE. In particular, we characterize PE defect levels in terms of thermodynamic and adiabatic charge transition levels that involve total energy calculations of neutral and charged defects. Calculations are performed at several levels of theory including those involving (semi)local and hybrid electron exchange-correlation functionals, and many-body perturbation theory. With these critical elements, the calculated defect transition levels are in excellent correspondence to observed luminescence spectra of PE, thus clarifying and confirming the origins of the observed peaks. Based on this work, a prescription with a reasonable computational expense is proposed to accurately predict and assign spectroscopic signatures of defects in other organic p
Caesium iodide is one of the more extensively studied scintillators. Here we present X-ray luminescence spectra, scintillation light output and decay curves as function of temperature, from room temperature down to below 10 K. Features of the observed intrinsic luminescence are explained in terms of radiative recombination of on- and off-centre STE. A model permitting interpretation of the dynamics of luminescence changes in CsI with temperature is suggested. This model includes adiabatic potential energy surfaces (APES) associated with singlet and triplet states of self-trapped excitons (STE) and explains the variation of the luminescence spectra with temperature as a result of re-distribution in the population between on- and off-centre STE. The temperature dependence of the scintillation light yield is discussed in the framework of the Onsager mechanism.